Tartaric Acid in Phosphorus Chemistry: Phosphor Emetics and

92 Tartaric Acid in Phosphorus Chemistry: Phosphor Emetics and Oligomers

Downloaded by UNIV OF CALIFORNIA SAN DIEGO on April 2, 2016 | http://pubs.acs.org Publication Date: November 11, 1981 | doi: 10.1021/bk-1981-0171.ch092

A. MUNOZ, L. LAMANDÉ, M. KOENIG, and R. WOLF E R A N° 926 Associée au CNRS, Laboratoire des Hétérocyeles du Phosphore et de Université Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse, France

l'Azote,

The complex of tartaric acid and antimony (emetic) was des cribed three centuries ago. Nevertheless, the structure of this compound has been elucidated these last fifteen years by X-ray diffraction (1). In fact, emetic presents a binuclear cyclic structure. Many authors mentioned similar complex with transition metals (vanadium (2), chromium (3)) or metalloids (arsenic (4), bismuth (5)). Emetic with phosphorus was not mentioned. Neverthe less, tartaric acid or alkyl tartrates has been utilized in phos phorus chemistry : tartaric acid reacts with trialkyl phosphites giving heterocyclic phosphites (6). Starting from alkyl tartra tes, we prepared spirophosphoranes with a P-H bond and sixcoordinated compounds (7). With unprotected tartaric acid, many possibilities appear : condensation as a diol, as a di(α-hydroxyacid), or even as a β-hydroxyacid. In fact, natural tartaric acid (R,R) reacts easily at room temperature with phosphorus trichloride. The main products of the reaction are spirophosphoranes with a P-H bond formed from the α-hydroxyacid linkage (scheme (A)).

We isolated two kinds of compounds : - After six hours (or less) of condensation, we obtained a white powder, soluble in THF, whose nmr spectrum and elemental analysis are consistent with the oligomer 1a. - When condensation time is higher than six hours, we isola ted a white powder insoluble in THF, whose spectrum, elemental analysis and molecular weight are consistent with the cyclic dimer 2a. 0097-6156/81/0171-0447S05.00/0 SOCIETY LIBRARY

1151 16th S i N. if. WwWAflton, 0. C. 20038

Quin and Verkade; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

448

PHOSPHORUS

HO-CO

Co-Ox, ? /O-CO

CO-OH

-O-CO

CO-O

-O-CH

~" -CH-O"

CHEMISTRY

f

v

x

,Ο,ΙΤΗΤ

,2 THF HO-CH

•CH-σ

O-CH n—CH-OH


la

λ

/

: 2 ^ 6

N

2a

S t a r t i n g w i t h t h e s e compounds, we s y n t h e t i s e d t h e c o r r e s p o n d i n g o l i g o m e r o r d i m e r h y d r o x y p h o s p h o r a n e s and a d d u c t s w i t h a n h e x a c o o r d i n a t e d p h o s p h o r u s atom, a c c o r d i n g t o r e a c t i o n s (B) and (C). OH...DMF -SMe -O-CO CO-0, ι -O-CO CO-Ov -1 ,CH„ ~DMF ι ι ΝΑΊ -O-CH; — C H - C T ^ 'CH. -O-CH CH-0 2

1,2a

η NEt

1,2b

η NEt,

3

(B) -O-CO ι I l-O-CH

(C) HNEt' CO-0, /

J

>/Α,

I CH-O /\ x

V i n

-O-CO

0~" HNEt CO-Ov 1 Λ

1 -O-CH

I X CH-(T

3 : η = 2

1 x

1,2b' #

f o r oligomers terminal omitted.

groups

On t h e o t h e r h a n d , c o n d e n s e d s p i r o p h o s p h o r a n e s la_ a n d 2 a a r e d e p r o t o n a t e d , u n d e r m i l d c o n d i t i o n s , by t r i e t h y 1 a m i n e , g i v i n g a n e q u i l i b r i u m b e t w e e n p h o s p h o r a n i d e and p h o s p h i t e a n i o n s , q u i t e s i m i l a r t o t h a t observed p r e v i o u s l y w i t h monomolecular phosphora nes (scheme (D)) ( 8 ) . u

HNEt.

Ν

-O-CO -O-CO

CO-0

-O-CH

CH-0 1,2a

ι

1

+ η

CO-0

NEt. -O-CH-

JH-O

χ

X

(D) -O-CO

CO-0

HNEt.

-O-CH

(L-0- -PI

J


MUNOZ E T A L .

Tartaric

Acid

in Phosphorus

Chemistry


92.


449


450

PHOSPHORUS CHEMISTRY

Figure 2.

Dimers 2a and 2b.

Figure 3.

Hexaeoordinated

adduct 3.


92.

MUNOZ ET AL.

Tartaric

Acid

in

Phosphorus

Chemistry

451


A n a l y s i s o f nmr s p e c t r a a l l o w e d us t o d e t e r m i n e t h e a b s o l u t e c o n f i g u r a t i o n o f t h e p h o s p h o r u s atom o f p e n t a c o - o r d i n a t e d com pounds l a , 2a and l b , 2b. P r o t o n s P-0-CH-CH-O-P and e x o c y c l i c s u b s t i t u e n t s P-H and P-0 Χ (X = H...DMF, HNEt^j) a r e i n a c i s p o s i t i o n . The more l i k e l y s t r u c t u r e o f o l i g o m e r s l a and Lb i s a s e q u e n c e o f TBP drawn up as h e l i x ( f i g . 1 ) , w h i l e d i m e r s 2ja and 2b s h o u l d p r e s e n t an e m e t i c s t r u c t u r e w i t h a p e n t a c o - o r d i n a t e d p h o s p h o r u s atom ( f i g . 2 ) . A l l t h e s e compounds m a n i f e s t s t r o n g o p t i c a l a c t i v i t y . These r e s u l t s complete t h e c h e m i s t r y o f t h e t a r t a r i c a c i d through elements o f p e r i o d i c c l a s s i f i c a t i o n . I f adducts between p h o s p h o r u s and t a r t a r i c a c i d have b e e n l a s t l y d i s c o v e r e d , t h e y o f f e r , i n r e t u r n , a l a r g e r c o - o r d i n a t i o n v a r i e t y than emetics which e x h i b i t e x c l u s i v e l y t e t r a c o - o r d i n a t i o n . I t i s i n t e r e s t i n g to n o t i c e that r e a l phosphorus emetic, spirophosphoranide a n i o n , i s r a t h e r u n s t a b l e i n c o n t r a s t w i t h t h e a r s e n i c o r a n t i m o n y homo l o g u e s , w h i l e p e n t a c o - o r d i n a t e d o r s i x c o - o r d i n a t e d compounds, w h i c h a r e s t a b l e , a r e unknown f o r t h e s e m e t a l l o i d s . Concerning phosphorus c h e m i s t r y , t h e s y n t h e s i s o f condensed compounds, o p t i c a l l y a c t i v e , w i t h p e n t a c o - o r d i n a t e d p h o s p h o r u s a d o p t i n g hélicoïdal o r m a c r o c y c l i c s t r u c t u r e s , r e p r e s e n t s , i n o u r o p i n i o n , s i g n i f i c a n t p r o g r e s s . T h u s , h y d r o x y p h o s p h o r a n e s l b , 2b a r e tautomers o f hydroxyphosphoric e s t e r s , s i m i l a r t o p h o s p h o r i c e s t e r s o f n a t u r a l p o l y h y d r o x y l a t e d compounds.

LITERATURE CITED

1. KIOSSE, G.A. ; GOLOVASTIKOV, N.I.; BELOV, N.V. Soviet. Phys. Doklady. 1964, 9, 198. 2. ORTEGA, R.B.; CAMPANA, C.F.; TAPSCOTT, R.E. Acta Cryst. 1980, Β 36, 1786, and references there in. 3. KAIZAKI, S.; HIDAKA, J.; SHIMURAI, Y. Bull. Soc. Chim. Jap. 1967, 40, 2207 4. SCHLESSINGER, G.; Inorg. Synth. 1970, 12, 267, and references there in. 5. ROSENHEIM, A.; VOGELSANG, W. Z. Anorg. Chem. 1906, 48, 205 6. SAMITOV, YU.YU.; MUSINA, A.A.; GURARII, L . I . ; MUKMENEV, E.T.; ARBUSOV, B.A. Bull. Acad. Sci. USSR 1975, 24, 1407, and refe rences there in. 7. KOENIG, M.; MUNOZ, A.; GARRIGUES, Β.; WOLF, R. Phosphorus and Sulfur 1979, 6, 435 8. GARRIGUES, Β.; KOENIG, M.; MUNOZ, A. Tetrahedron Letters 1979, 4205 RECEIVED

July 7,

1981.


Tartaric Acid in Phosphorus Chemistry: Phosphor Emetics and

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