Organometallic Derivatives of Sucrose as Pesticides RC POLLER and

11

Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 28, 2018 | https://pubs.acs.org Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0041.ch011

Organometallic Derivatives of Sucrose as Pesticides

R. C. POLLER and A. PARKIN Chemistry Department, Queen Elizabeth College, University of London, Campden Hill Rd., London W8 7AH, England

Organotin p e s t i c i d e s , u s u a l l y containing three t i n c a r b o n bonds ( R S n X ) , a r e u n i q u e i n t h a t b i o l o g i c a l a c t i v i t y d i s a p p e a r s when t h e o r g a n i c g r o u p s a r e removed from t h e m e t a l . T h i s p r o c e s s o c c u r s on e x p o s u r e t o l i g h t and m i c r o o r g a n i s m s (1,2) and t h e s e p e s t i c i d e s , t h e r e f o r e , p r e s e n t no t h r e a t t o t h e e n v i r o n m e n t . Their major d i s a d v a n t a g e s a r e h i g h c o s t and l a c k o f s p e c i f i c i t y s o t h a t p r e y a s w e l l a s p r e d a t o r , may b e a t t a c k e d . The a i m o f t h e p r e s e n t w o r k w a s t o e x a m i n e t h e e f f e c t on b i o l o g i c a l a c t i v i t y o f m a k i n g a major change i n t h e s o l u b i l i t y o f R S n X compounds by i n t r o d u c i n g a sucrose residue i n t o the X group. T h i s method o f i n c r e a s i n g s o l u b i l i t y seemed a t t r a c t i v e s i n c e g l y c o s i d e f o r m a t i o n commonly i s u s e d i n n a t u r e t o e f f e c t t r a n s port i n tissue c e l l s of otherwise insoluble materials. Because o f the nature o f the f u n c t i o n a l groups p r e s e n t i n c a r b o h y d r a t e s , few o f t h e i r o r g a n o m e t a l l i c d e r i v a t i v e s have been r e p o r t e d . Organotin groups have been l i n k e d t o c e l l u l o s e by a v a r i e t y o f methods (3,4). I n a few i n s t a n c e s h y d r o g e n atoms o f h y d r o x y l groups i n sugars have been r e p l a c e d by o r g a n o t i n groups (5-7) b u t t h e s e a l k o x y d e r i v a t i v e s u s u a l l y a r e s e n s i tive to water. M o r e r e c e n t l y , we h a v e d e s c r i b e d some more s t a b l e compounds i n w h i c h an o r g a n o m e t a l l i c g r o u p i s j o i n e d t o a sugar by a s u l p h u r atom (8). None o f t h e s e m e t h o d s seemed a p p r o p r i a t e t o o u r p u r p o s e a n d we d e c i d e d t o p r e p a r e o r g a n o t i n c o m p o u n d s from s u c r o s e hydrogen p h t h a l a t e and s u c r o s e hydrogen s u c c i n a t e , s i n c e t h e s e c o u l d be o b t a i n e d by d i r e c t r e a c t i o n s between s u c r o s e and p h t h a l i c o r s u c c i n i c a n h y d r i d e s , as shown i n F i g u r e 1. The m a l e a t e was d i f f i c u l t t o i s o l a t e so t h a t l a t e r w o r k was c o n f i n e d t o the p h t h a l a t e and s u c c i n a t e . 3

3

145

Hickson; Sucrochemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

146

SUCROCHEMISTRY

sucroseOH + X


N

X

^COOsucrose COOH

+

CO

R M OH

CH -

I

J->

2

2

CH 2

HC-

• I

HC-

X

COOsucrose ÖDOH COOsucrose

NrcoMRg

M=Ge,Sn,Pb

Figure 1

We w e r e i n t e r e s t e d i n c o m m e r c i a l e x p l o i t a t i o n a n d c h o s e t o use f r e e s u c r o s e and a c c e p t t h a t , i n a d d i t i o n to v a r i a t i o n s i n the e x t e n t of s u b s t i t u t i o n , there w o u l d be c o m p l i c a t i o n s due t o r e g i o i s o m e r i s m . A l l of the b i o l o g i c a l t e s t s were c a r r i e d out w i t h the crude p r o d u c t s o b t a i n e d from the above r e a c t i o n s . Before g i v i n g d e t a i l s of the r e s u l t s of these t e s t s , r e f e r e n c e w i l l be made t o some a s p e c t s o f t h e w o r k we h a v e d o n e on c h e m i c a l c h a r a c t e r i s a t i o n o f t h e s u c r o s e e s t e r s . W i t h r e g a r d t o t h e d e g r e e o f s u b s t i t u t i o n , two approaches have been u s e d , i . e . s e p a r a t i o n o f s i l y l a t e d d e r i v a t i v e s by gas c h r o m a t o g r a p h y ( g l c ) w i t h mass s p e c t r o g r a p h s e x a m i n a t i o n o f t h e p e a k s and s e p a r a t i o n o f a c e t y l d e r i v a t i v e s by column c h r o m a t o g r a p h y . A typic a l g l c t r a c e i s shown i n F i g u r e 2. From r i g h t t o l e f t , t h e f i r s t p e a k i s due t o s o l - v e n t , t h e n e x t s h a r p peak i s o c t a ( t r i m e t h y l s i l y l ) s u c r o s e and t h e s i l y l a t e d s u c r o s e s u c c i n a t e s t h e n appear as a p o o r l y r e s o l v e d , composite peak. H e n c e , a l t h o u g h we c a n a c u r a t e l y e s t i m a t e t h e a m o u n t o f u n s u b s t i t u t e d s u c r o s e , we a r e l e s s c e r t a i n o f t h e r e l a t i v e a m o u n t s o f mono- a n d d i ester. The s e c o n d t e c h n i q u e , w h e r e b y s u c r o s e o c t a a c e t a t e and t h e v a r i o u s a c e t y l a t e d s u c r o s e e s t e r s a r e s e p a r a t e d by c o l u m n c h r o m a t o g r a p h y , y i e l d s more r e l i a ble information. I n T a b l e s I a n d I I t h e two m e t h o d s a r e c o m p a r e d a n d we s e e t h a t a g r e e m e n t i s g o o d i n t h e c a s e o f t h e p h t h a l a t e e s t e r , l e s s so f o r t h e s u c c i n a t e and t h a t b o t h p r o d u c t s c o n t a i n s u b s t a n t i a l amounts o f free sucrose.


11.

POLLER

AND PARKIN

Organometallic Derivatives

147


!

Figure 2. GLC trace of "sucrose succinate" after trimethylsilylation

Table I C o m p o s i t i o n o f Sucrose

Phthalate Method

Free sucrose Monoester Diester Higher e s t e r s

Separation o f Acetates (%) 36 37 26 1

Separation o f Me Si derivs. (%) 35 42 24 0 3

American Chemical Society Library

w.

1155 16th St. N. Hickson; Sucrochemistry Washington, D. C. Chemical 200%Society: Washington, DC, 1977. ACS Symposium Series; American

148

SUCROCHEMISTRY

Table I I Composition

of Sucrose

Succinate


Method Separation of Acetates (%) 22 43 34 1

Free sucrose Monoester Diester Higher e s t e r s

Separation of Me~Si d e r i v s . (%) 32

3

65 3

We a r e n o t i n a p o s i t i o n t o make a n y p r e c i s e s t a t e m e n t s a b o u t r e g i o i s o m e r i s m w i t h i n t h e mono- a n d d i e s t e r c l a s s i f i c a t i o n s b u t i n f o r m a t i o n c a n be g l e a n e d f r o m a somewhat s p e c u l a t i v e i n t e r p r e t a t i o n o f t h e l ^ C nmr ( n u c l e a r m a g n e t i c r e s o n a n c e ) s p e c t r a o f t h e s e p r o ducts. Work i n t h i s a r e a s t i l l i s i n p r o g r e s s a n d , f o r example, our t e n t a t i v e c o n c l u s i o n r e g a r d i n g sucrose p h t h a l a t e i s t h a t s u b s t i t u t i o n has o c c u r r e d a t the 6,6' a n d 4 p o s i t i o n s i n s u c r o s e . I t was o f i n t e r e s t t o i n c l u d e i n o u r b i o l o g i c a l t e s t s a compound i n w h i c h t h e s u c r o s e r e s i d u e was i n c o r p o r a t e d i n t o a n R g r o u p o f a n R^SnX c o m p o u n d . To t h i s e n d we u t i l i s e d t h e s e r i e s o f r e a c t i o n s shown i n F i g u r e 3, b e g i n n i n g w i t h t h e s o d i u m s a l t o f t h e c r u d e sucrose phthalate. Given the complexity of the s t a r t i n g m a t e r i a l , t h e f i n a l bromo compound, o f c o u r s e , i s a m i x t u r e b u t i t s a n a l y s i s , i n f r a r e d ( i r ) a n d nmr s p e c t r a c o r r e s p o n d t o t h e f o r m u l a shown. Cœsucrose ^SnCH CH CH Br

-f-

2

2

2

— ^

COONa

^.COOsucrose ^\:OOC

^COOsucrose

H £ H C H SnPh 2

2

3

^ ^ C O O C H

2

C H CH SnPh Br 2

2

2

Figure 3

T u r n i n g now t o t h e b i o l o g i c a l a c t i v i t y o f t h e s e compounds t h e r e s u l t s o f t e s t s a g a i n s t v a r i o u s o r g a n isms a r e summarized i n T a b l e s I I I - V I .


11.

POLLER


AND PARKIN

Table I I I

Activities

149

against paint-destroying No. o f f u n g i s h o w i n g of spore germination

Compound

inhibition (max 16) 1

i

Bu SnOCOC H COOsucrose

16

16

6

P h - SnOCOC^H„COO s u c r o s e 3 6 4

16

14

4

0

0

3


10 ppm

100 ppm

fungi

6

(C H 6

1 ; L

4

) SnOCOC H COOsucrose 3

6

4

3

Bu SnOCOCH CH COOsucrose

16

16

10

Ph SnOCOCH CH COOsucrose

16

15

9

SucroseOCOC^H-COO(CH ) SnPh Br

16

7

0

(Bu Sn) 0

13

13

12

3

2

3

2

2

2

0

6

4

2

3

9

3

2

Table IV A c t i v i t i e s a g a i n s t E n t e r o m o r p h a : compounds t e s t e d against Enteromorpha i n seawater modified w i t h algal nutrients.

Concentration Compound

1 ppm

Bu^SnOCOC^H ..COOsucrose 3 6 4 Ph^SnOCOC^H.COOsucrose 3 6 4

0.1 ppm

+

+

+

+

Bu SnOCOCH CH COOsucrose

+

+

Ph SnOCOCH CH COOsucrose

+

+

C

H

^ 6 11^3 3

S

n

O

C

2

3

O

C

H

6 4

C

O

O

s

u

c

r

O

S

e

2

2

2

SucroseOCOC^H.COO(CH )~SnPh Br 9

b

q

z

J

2

+=effective

+

+

-=not e f f e c t i v e

M i n i mmm u m cconcG oncentration

a t which

(Bu Sn) 0 i s effective 3

2

0.3 ppm


150

SUCROCHEMISTRY

Table

V.

Antibacterial

properties of organotin Escherichia coli


Compound

31

P h - SnOCOC ^ H„COO s u c r o s e 3 6 4

Cone (ppm)

Inhib

84

100

7%T

Bu SnOCOC H COOsucrose 3

6

4

SucroseOCOC^H-COO(CHJ SnPh Br 6

2

4

2

compounds Micrococcus denitrificans

1 1

11

Cone (ppm)

Inhib (%)

0.25

100

1

100

1

100

1 1

3

23

83

Table VI Molluscicidal

Activity

Compounds t e s t e d a g a i n s t a d u l t B i o m p h a l a r i a c f l a b r a t a . The L C 5 0 a s s e s s e d a f t e r a 120 h r e c o v e r y p e r i o d . Compound T r i p h e n y l l e a d Sucrose P h t h a l a t e T r i p h e n y l t i n Sucrose P h t h a l a t e T r i p h e n y l l e a d Sucrose Succinate T r i c y c l o h e x y l t i n Sucrose P h t h a l a t e T r i b u t y l t i n Sucrose P h t h a l a t e T r i p h e n y l t i n Sucrose Succinate T r i b u t y l t i n Sucrose Succinate

L C

50 Tppm) 0.1-0.2 0.2 0.1-0.2 0.05 0.1 >0.2 0.075-0.1

T h e s e r e s u l t s show t h a t t h e t r i b u t y l t i n a n d t r i phenyltin d e r i v a t i v e s o f sucrose are a t l e a s t equal i n b i o l o g i c a l a c t i v i t y t o t h e commercially used t r i b u t y l t i n o x i d e and f l u o r i d e and a r e s u p e r i o r w i t h r e g a r d t o a l g i c i d a l and f u n g i c i d a l p r o p e r t i e s (9/ 1 0 ) . This i s e v e n more r e m a r k a b l e when we c o m p a r e t h e t i n c o n t e n t s , see Table V I I . Except i n t h e case o f m o l l u s c i c i d a l a c t i v i t y t h e t r i c y c l o h e x y l t i n compounds a r e l e s s e f f e c t i v e a n d , i n most t e s t s , t h e l e s s a c c e s s i b l e compound w i t h t h e s u c r o s e r e s i d u e i n t h e R g r o u p s is inferior. T e s t s o n t h e o r g a n o l e a d compounds so f a r have b e e n c o n f i n e d t o m o l l u s c i c i d a l a c t i v i t y .


11.

P O L L E R A N D PARKIN


151

Table V I I


Tin content

of biocidal organotin

Compound

% Sn

T r i b u t y l t i n oxide Tributyltin fluoride Bu3SnOCOC5H4COO s u c r o s e Ph3SnOCOC5H4COO s u c r o s e

39.8 38.4 15.2 14.1

compounds

T r i b u t y l t i n sucrose p h t h a l a t e and s u c c i n a t e have been f o r m u l a t e d i n t o p a i n t s and s u b j e c t e d t o l a r g e r scale tests. The f u n g i c i d a l a c t i v i t y i s r e t a i n e d and t h e compounds a p p e a r t o g i v e e n h a n c e d p r o t e c t i o n t o w e a t h e r e d f i l m s o f e m u l s i o n p a i n t when c o m p a r e d w i t h t r i b u t y l t i n oxide. I n t h e t r i a l k y l a n d t r i p h e n y l compounds d e s c r i b e d above t h e sucrose group i s j o i n e d t o t i n v i a an f

-Sn-OCO-Ç- g r o u p . A l t h o u g h t h e b i o l o g i c a l t e s t s and o t h e r measurements i n d i c a t e t h a t t h i s g r o u p i s much m o r e r e s i s t a n t t o h y d r o l y s i s than might be expected, i t , n e v e r t h e l e s s , r e p r e s e n t s a p o i n t o f s t r u c t u r a l weakness i n t h e molecule. We t h e r e f o r e , h a v e b e e n e x a m i n i n g o t h e r m e t h o d s of j o i n i n g o r g a n o t i n groups t o sucrose, again c o n f i n i n g ourselves t o processes o f p o t e n t i a l commercial interest. The m o s t e f f e c t i v e o f t h e s e i s a s f o l l o w s : R S n S C H C O O M e + s u c r o s e O H - > R S n S C H C O O s u c r o s e + MeOH 3

2

3

2

As b e f o r e , t h e p r o d u c t l i k e l y i s t o be a m i x t u r e a n d we a s y e t d o n o t h a v e d e t a i l s o f i t s c o m p l e x i t y . The f u n g i c i d a l p r o p e r t i e s o f t h i s t y p e o f compound a r e being evaluated. Preliminary results indicate that t h e y a r e somewhat l e s s a c t i v e t h a n t h e p h t h a l a t e s a n d s u c c i n a t e s , b u t b e t t e r t h a n t r i b u t y l t i n o x i d e , on a weight f o r weight b a s i s . Acknowledgements We t h a n k t h e I n t e r n a t i o n a l S u g a r R e s e a r c h F o u n d a t i o n , I n c . , f o r s u p p o r t i n g t h i s work. We a r e g r a t e f u l to t h e P a i n t Research A s s o c i a t i o n f o r c a r r y i n g o u t t h e t e s t s a g a i n s t f u n g i a n d E n t e r o m o r p h a , t o D r . P. N o r r i s ( M i c r o b i o l o g y D e p a r t m e n t , Queen E l i z a b e t h C o l l e g e ) f o r c a r r y i n g o u t t h e t e s t s a g a i n s t b a c t e r i a and t o Dr. J Duncan ( C e n t r e f o r O v e r s e a s P e s t R e s e a r c h ) f o r t h e molluscicidal screening.


152

SUCROCHEMISTRY

Abstract Methods for attaching organotin groups to sucrose are discussed. Treatment of sucrose with phthalic (or succinic) anhydride gave a mixture of sucrose hydrogen phthalates (succinates) which reacted with organotin hydroxides, (RSnOH R=alkyl or aryl), to give organostannyl sucrose phthalates (succinates). The corresponding organolead and organogermanium compounds were prepared by similar methods. The biocidal activities of the organotin derivatives of sucrose were found to be much higher than would be expected from the tin content.


3

Literature Cited 1.

Barnes, R.D., Bull, A. T., Poller, R.C., Pestic. S c i . , 1973, 4, 305. 2. Chapman, A. H., Price, J . W., Int. Pest Control, 1972, 14, 11. 3. Shostakovskii, M. F . , Polyakov, A. I . , Sinagin, V. V., Mirskov, R. G., Zh. P r i k l . Khim., 1968, 41, 2796. 4. Arcemova, Yu V . , Vinnik, A. D., Zemlyanskii, N.W., Rogevin, Z. A . , Cellulose Chem. Technol., 1971, 5, 319; (Chem. Abs., 1972, 76, 155815.) 5. David, S., and Thieffry, A . , C.R. Hebd. Seances, Acad. Sci. Ser. C., 1974, 279, 1045. 6. Wagner, D., Verheyden, J . P. H., and Moffatt, J.G. J . Org. Chem., 1974, 39, 24. 7. Crowe, A. J., and Smith, P. J., J . Organomet. Chem. 1976, 110, C59. 8. Husain, A. F., and Poller, R. C., J . Organomet. Chem., 1976, 118, C11. 9. Parkin, A., and Poller, R.C., British Patent Application No. 12168/76. 10. Parkin, A . , and Poller, R.C., Pesticide Science, in press. Biographic Notes Robert C. Poller, Ph.D., Reader in Chem. Educated at Univ. of Southampton. Chemist in the food industry; post-doctoral work at Birkbeck C o l l . ; organometallic chemistry and polymer stabilization. The Chemistry Department, Queen Elizabeth C o l l . , Univ. of London, Atkins Building, Campden H i l l Road, London W.8, England.



Discussion

Question: Mr. K o s a k a , y o u r s u g a r e s t e r s w e r e duced u s i n g a s o l v e n t . What s o l v e n t d i d y o u u s e ? DMF?

pro-

Mr. K o s a k a : R y o t o d o e s n o t u s e DMF, b u t I do n o t d e n y t h a t t h e c o m p a n y i s u s i n g some k i n d o f s o l v e n t i n the process. Question: toxic?

I s i t an

edible solvent,

Mr. K o s a k a : I t i s one o f t h e s a f e s t however, the p r o d u c t s are s o l v e n t - f r e e .

and

i s i t non-

solvents,

Question: Dr. P a r k e r , have you done any e x p e r i ments i n m a k i n g y o u r s u g a r e s t e r by the s o l v e n t l e s s process u s i n g impure sugar r a t h e r than pure sucrose? I f so, what r e s u l t s d i d you g e t ? Dr. P a r k e r : We h a v e u s e d i m p u r e s u g a r b u t n o t m o l a s s e s , w h i c h h a s t o o h i g h an a s h c o n t e n t . The m a i n r e a s o n f o r not d o i n g so i s t h a t t h e s u g a r r e p r e s e n t s a r e l a t i v e l y m i n o r c o s t c o n s t i t u e n t , and traditionally we h a v e u s e d r e f i n e d s u g a r . We do n o t h a v e t o , b u t t h e r e i s no p a r t i c u l a r a d v a n t a g e i n n o t d o i n g s o . Question: M o n s i e u r B o b i c h o n , c o u l d you d i v u l g e some g e n e r a l way how y o u m a n a g e d t o r e d u c e t h e d i m e t h y l f o r m a m i d e t o 5 ppm?

in

Mr. B o b i c h o n : I c a n n o t a n s w e r t h a t i n t o o much d e t a i l - j u s t by t a k i n g p a i n s i n t h e p r o c e s s , being very c a r e f u l . I do n o t t h i n k t h a t t h e d i m e t h y l f o r m a m i d e i s r e a l l y s u c h a bad m a t e r i a l , and I a g r e e w i t h what Dr.Hass s a i d t h i s m o r n i n g about the i n a p p r o p r i a t e 153


154

SUCROCHEMISTRY

ness of

zero

tolerance for toxic materials.

Question;

What i s m e a n t b y

a half-day

diarrhea?


Mr. B o b i c h o n : We m e a s u r e t h e d i a r r h e a o f t h e a n i m a l s t w i c e a day by v i s u a l e v a l u a t i o n , and r e c o r d t h e t o t a l number o f o b s e r v a t i o n s and t h e number o f d e f i n i t e diarrhea. Question;

Is that after

84

Mr. B o b i c h o n ; A f t e r 84 d a y s 168 e v a l u a t i o n s . As a n e x a m p l e , positive diarrhea observations. 14 a s t h e n u m b e r f o r t h e h a l f - d a y

days of

feeding?

o f f e e d i n g , we h a v e we c o u l d h a v e 14 T h e n we w o u l d r e c o r d diarrhea.

Question; How d o t h e e c o n o m i c s o f t h e t h r e e f a c t a n t s compare w i t h t h e p e t r o c h e m i c a l l y - d e r i v e d d u c t s , on a c o s t / p e r f o r m a n c e b a s i s ?

surpro-

Dr. P a r k e r ; I t i s v e r y d i f f i c u l t t o answer f o r other processes. Our own w o r k was b a s e d on t h e f a c t t h a t we w i s h e d t o o b t a i n a s u c r o s e - d e r i v e d s u r f a c t a n t w h i c h was i n d e e d c o m p e t i t i v e w i t h l i n e a r alkylbenzene sulfonate-types of surfactants. Our p r o d u c t , a s p r o d u c e d a t t h e moment, i s somewhat c h e a p e r . We a l s o have a r a n g e o f more h i g h l y p u r i f i e d p r o d u c t s w h i c h a r e m o r e e x p e n s i v e , b u t a r e i n t e n d e d t o be c o m p e t i t i v e w i t h n o n - i o n i c s u r f a c t a n t s of the s o r b i t a n e s t e r - t y p e . I t h i n k p r o c e s s e s u s i n g s o l v e n t s i n e v i t a b l y m u s t be somewhat more e x p e n s i v e , b e c a u s e o f t h e n e e d t o r e d u c e s o l v e n t r e s i d u e s t o a minimum. We w e r e n o t a b l e t o s e e how we c o u l d do t h i s , b u t m a y b e , M o n s i e u r B o b i c h o n , could give h i s p o i n t of view. Mr. B o b i c h o n ; I t i s d i f f i c u l t for a surfactant to be c o m p e t i t i v e p r i m a r i l y b e c a u s e o f t h e pH s t a b i l i t y . We t r i e d many t i m e s t o f i n d a p p l i c a t i o n s i n s u r f a c t a n t s f o r o u r s u c r o g l y c e r i d e , b u t we f a i l e d b e c a u s e o f t h e i n s t a b i l i t y a t a l k a l i n e pH. Question; please?

Dr.

Parker, w i l l

you

comment on

that,

Dr. P a r k e r ; We f o u n d t h a t t h e s u c r o g l y c e r i d e s a r e s t a b l e o v e r a pH r a n g e f r o m 6 t o 1 2 . Obviously, they are not s t a b l e under a c i d i c c o n d i t i o n s , a n d t h i s c o n s t i tutes a limitation. B u t , t h e number o f a p p l i c a t i o n s r e q u i r i n g a c i d - s t a b l e s u r f a c t a n t s are r e l a t i v e l y few. We a r e n o t w o r r i e d b y t h i s , a l t h o u g h we w o u l d l i k e t o


155

DISCUSSION

h a v e one

f o r these p a r t i c u l a r

applications.

Question: Mr. K o s a k a , w o u l d y o u l i k e t h i n g about the economics of your product?

t o say

any-


Mr. K o s a k a : The r e c o v e r y o f s o l v e n t i n t h e R y o t o p r o c e s s i s g r e a t e r t h a n 99%. Thus, the c o s t of s o l v e n t i s n e g l i g i b l e , and o u r p r o d u c t s a r e s o l v e n t - f r e e . Question: Mr. K o s a k a , w o u l d you e l a b o r a t e on bakery uses of sucrose e s t e r s i n Japan?

the

Mr. K o s a k a : The u s e i n c a k e s i s m o s t p o p u l a r . J a p a n e s e b a k e r s a r e u s i n g a m i x t u r e o f s u g a r e s t e r and monoglyceride i n bread. Question: For high protein breads, or just l a r wheat bread? Mr.

Kosaka:

Question: agent? Mr.

Kosaka:

Just regular

bread.

I s t h a t a p p l i c a t i o n as an

Y e s , as an a n t i - s t a l i n g

Q u e s t i o n : How d i f f i c u l t i s s i d u a l methanol content,and the anol? I f t h e r e i s any p r o b l e m , use o f t h e e t h y l e s t e r s f o r the

regu-

anti-staling

agent,mostly.

i t to c o n t r o l the r e t o x i c i t y o f t h i s methhave you thought o f the transesterification?

Mr. K o s a k a : We t h o u g h t a b o u t u s i n g e t h y l e s t e r , but i t s cost i s higher than that of methyl ester. We cannot f i n d methanol i n our products. Dr. Hass: Minute t r a c e s o f methanol are not t o x i c . The p e c t i n s w h i c h a r e u s e d f o r m a k i n g j e l l i e s h a v e c a r bomethoxy groups w h i c h a r e s p l i t o f f i n t h e d i g e s t i v e s y s t e m t o f o r m t r a c e s o f m e t h a n o l , a n d t h e y do n o t h u r t anybody. Dr. H i c k s o n : W i t h r e g a r d t o t h e e t h a n o l - m e t h a n o l question,do not forget that ethanol b o i l s at a s l i g h t l y h i g h e r t e m p e r a t u r e and r e q u i r e s a l i t t l e more h e a t t o take i t o f f . The r e a c t i o n c a l l s f o r t h e d i s t i l l a t i o n of methanol t o p r o v i d e the d r i v i n g force t o create the sugar e s t e r . T h a t i s a m a j o r r e a s o n why t h e m e t h y l e s t e r was c h o s e n . Question:

P r o f e s s o r S e i b , what i s t h e

potential


156

SUCROCHEMISTRY


t o t a l volume o f t h e s u r f a c t a n t market, i n b a k i n g , i n the u n i t e d S t a t e s , alone? Professor Seib: I t r i e d t o i n t i m a t e what t h e t o t a l m a r k e t m i g h t be by t a b u l a t i n g t h e poundage o f t h e v a r i o u s baked foods i n t h e United S t a t e s . I f 70% o f t h a t poundage i s b r e a d and r o l l s , one c o u l d estimate a b o u t 90,000 l b / d a y o f s u r f a c t a n t f o r t h a t p a r t o f t h e market. The n e x t l a r g e s t u s e p r o b a b l y w o u l d b e c a k e . I c a l c u l a t e d a n o t h e r 10,000 l b o f e s t e r / d a y i n t h a t market. T h a t i s b a s e d o n a t o t a l o f 1.4 b i l l i o n l b of cake a n n u a l l y , which c o n t a i n s 3 t o 6 % s u r f a c t a n t i n t h e e m u l s i f i e d s h o r t e n i n g s w h i c h a r e u s e d i n c a k e manufacturing. I think that, c e r t a i n l y , i s not the t o t a l , b u t y o u c a n s e e how q u i c k l y y o u d r o p o f f i n m a g n i t u d e f r o m 14 - 17 b i l l i o n l b o f b r e a d a n d r o l l s down t o 1.4 b i l l i o n l b o f cake p e r year. I think that a potential m a r k e t o f a 100,000 l b / d a y o f s u g a r e s t e r s i n t h e baki n g i n d u s t r y i s a f a i r l y good a p p r o x i m a t i o n . M r . B e a t t y , o f C o n t i n e n t a l B a k i n g , h a s j u s t m e n t i o n e d t h a t 450,000 t o n s o f b r e a d f l o u r / y e a r i s u s e d b y h i s company a l o n e . Question; Dr. van V e l t h u i j s e n , i s t h e p r i c e o f t h e s u g a r a l c o h o l s much h i g h e r t h a n t h e p r i c e o f s u g a r ? How d o e s t h i s a f f e c t t h e t o t a l e c o n o m i c s o f t h e f i n a l product? Dr. v a n V e l t h u i j s e n ; The p r i c e o f t h e s u g a r a l c o h o l s i s about double o r t r i p l e t h e p r i c e o f sugar. Of course, t h i s enters i n the costing of the product. Even s o , t h e p r i c e o f t h e crude r e a c t i o n m i x t u r e i s i n t h e same p r i c e l e v e l a s t h e s u r f a c t a n t s , s u c h a s t h e g l y c e r o l m o n o s t e a r a t e s a n d s t e a r o y l l a c t y l a t e s , now a v a i l a b l e i n t h e foods market. Question; D r . P o l l e r , a r e t h e r e a n y p l a n s t o go f o r w a r d w i t h f i e l d t e s t i n g o f any o f t h e p e s t i c i d e s you m e n t i o n e d ? Dr. P o l l e r ; A s I i n d i c a t e d i n my t a l k , t h i s h a s been done f o r a p p l i c a t i o n s i n p a i n t s . Large-scale t e s t s have been c a r r i e d o u t . F o r more g e n e r a l u s e s — f o r i n s t a n c e , i n a g r i c u l t u r e — we a r e a t p r e s e n t j u s t coming t o t h e end o f s y n t h e s i z i n g l a r g e - s c a l e batches for e x a c t l y t h i s purpose. Professor V l i t o s ; The s c r e e n i n g o f compounds o f t h i s type i s rather d i f f i c u l t . The s y n t h e s e s u s u a l l y a r e done i n a u n i v e r s i t y l a b o r a t o r y , u s u a l l y i n t h e c h e m i s t r y d e p a r t m e n t , and t h e s c r e e n i n g h a s t o be done


157


DISCUSSION

by b i o l o g i c a l g r o u p s . Very o f t e n they are busy doing t h e i r own t y p e s o f r e s e a r c h . I f t h e r e i s any weakness i n the approach o f the I n t e r n a t i o n a l Sugar Research F o u n d a t i o n i t i s t h a t i t has b e e n f o u n d t o be v e r y d i f f i c u l t t o s c r e e n t h e u s e f u l n e s s o f t h e compounds t h a t have been s y n t h e s i z e d i n t h e r e s e a r c h programs. T h e r e a r e many, many c o m p o u n d s , w h i c h may h a v e , who k n o w s how many a p p l i c a t i o n s . We j u s t h a v e n o t h a d a c h a n c e t o r e a l l y l o o k a t them a l l i n t h e r i g h t t e s t systems. I t h i n k Dr. P o l l e r ' s work i n d i c a t e s : f i r s t , h e r e i s some i n t e r e s t i n g c h e m i s t r y ; a n d s e c o n d , h i s compounds h a v e a u s e w h i c h a l r e a d y h a s b e e n d e m o n s t r a t ed. Now, i t i s up t o somebody t o s y n t h e s i z e t h e m a n d s e l l them. That i s another problem. Question: Dr. P o l l e r a r e these m a t e r i a l s s o l u b l e enough i n w a t e r t o use them, o r a r e t h e y c o m p l e t e l y solvent-soluble? Dr. P o l l e r : The s o l u b i l i t i e s o f t h e s t a n d a r d , o r g a n o t i n p e s t i c i d e s c u r r e n t l y i n use a r e low — some o f them v e r y l o w , i n d e e d — i n parts per m i l l i o n . By p u t t i n g o n t h e s u c r o s e g r o u p , t h e s o l u b i l i t y g o e s up a r o u n d a t h o u s a n d f o l d , a s a r o u g h e s t i m a t e , b u t we h a v e no p r e c i s e f i g u r e s . T h i s i s an i n t e r e s t i n g q u e s t i o n . Is t h i s simply a s o l u b i l i t y e f f e c t , or i s i t something e l s e ? I conclude i t i s not simply a s o l u b i l i t y e f f e c t because, a t l e v e l s where t h e t r i b u t y l t i n o x i d e i s s o l u b l e , t h e a c t i v i t i e s o f t h e s u c r o s e compounds a r e h i g h e r . In t h e b e s t t e s t s , t h e s u c r o s e compound i s t h r e e t i m e s more e f f e c t i v e w i t h a r o u n d a t h i r d t h e amount o f t i n i n it. Most o f t h e t e s t s were c a r r i e d o u t a t c o n c e n t r a t i o n s where b o t h t h e s u c r o s e compounds and t h e r e f e r ence o r g a n o t i n p e s t i c i d e s were c o m p l e t e l y d i s s o l v e d and s o t h e i n c r e a s e d a c t i v i t i e s c a n n o t s i m p l y be a t t r i buted t o s o l u b i l i t y e f f e c t s . Question: Would t h e h i g h s o l u b i l i t y culties i n formulation?

cause

diffi-

Dr. P o l l e r : Not n e c e s s a r i l y . The o r g a n o t i n e s t e r s c a n be h y d r o l y s e d and i t i s p o s s i b l e t h a t , a f t e r t r a n s p o r t i n l i v i n g t i s s u e as t h e o r g a n o t i n sucrose e s t e r , h y d r o l y s i s o c c u r s and t h e i n s o l u b l e o r g a n o t i n oxide i s then deposited.

these

Question: What k i n d o f b r e a k d o w n p r o d u c t s d o s u c r o s e t i n c o m p o u n d s h a v e o n biodégradation?


158

SUCROCHEMISTRY

Dr. P o l l e r : We do n o t know. The s u c r o s e t i n d e r i v a t i v e s a r e v e r y new,and t h e y s t i l l a r e b e i n g t e s t ed. H o w e v e r , we h a v e d o n e some w o r k o n biodégradat i o n of t r i p h e n y l t i n p e s t i c i d e s . T h i s was d o n e b y s y n t h e s i z i n g l C - l a b e l l e d p e s t i c i d e s , p u t t i n g them i n t o s o i l u n d e r v a r i o u s c o n d i t i o n s , and t h e n c o l l e c t i n g t h e r a d i o a c t i v e l y l a b e l l e d carbon dioxide. The organic g r o u p s come o f f i n a s t e p w i s e f a s h i o n a n d b r e a k down completely, to carbon dioxide. Only i n o r g a n i c t i n r e mains .


4

Question: I s i t d e f i n i t e l y i n o r g a n i c t i n , and some t i n - a l k y 1 d e r i v a t i v e s u c h a s a m e t h y l t i n compound?

not

Dr. P o l l e r : Yes. A l^C-labelled, radiochemicall y and c h e m i c a l l y p u r e compound i s a d d e d t o s o i l , and t h e r a d i o a c t i v i t y o f t h e 14co? e v o l v e d i s m e a s u r e d carefully. When a l l o f t h e 14c l a b e l a p p e a r s a s c a r b o n d i o x i d e t h e r e i s no d o u b t t h a t t h e c o m p o u n d i s b r o k e n down c o m p l e t e l y . T h i s i s t h e s o r t o f e v i d e n c e we have t h a t t h e t r i p h e n y l t i n compounds a r e c o n v e r t e d t o inorganic t i n . Question: A r e y o u c e r t a i n t h a t a n o r g a n o t i n comp o u n d c o u l d n o t f i n d i t s way i n t o t h e f o o d c h a i n some o t h e r way, p o s s i b l y t h r o u g h s o l u b i l i z a t i o n processes, t r a n s p o r t p r o c e s s e s , and so f o r t h ? Dr. P o l l e r : I t i s i m p o s s i b l e t o be c e r t a i n , b u t t h e e v i d e n c e we h a v e s u g g e s t s t h a t o r g a n o t i n p e s t i c i d e s a r e c o n v e r t e d t o i n o r g a n i c t i n on e x p o s u r e t o l i g h t and microorganisms. The w i d e u s e o f t i n - p l a t e d c a n s a s f o o d c o n t a i n e r s a n d much o t h e r e v i d e n c e i n d i c a t e s t h a t i n o r g a n i c t i n compounds a r e n o t t o x i c . Dr. Hass: I t was t h e i d e a o f one o f o u r librarians a t S u g a r R e s e a r c h F o u n d a t i o n t h a t t h e g e n e r a l app r o a c h o f c o m b i n i n g s u c r o s e w i t h p e s t i c i d e s m i g h t be effective. We f i r s t t r i e d i t i n a p r o j e c t a t B a t t e l l e f r o m w h i c h we n e v e r g o t a n y t h i n g t h a t was a s g o o d a s existing pesticides. I am d e l i g h t e d t h a t y o u a r e d o i n g i t , and t h a t we s i m p l y t r i e d t h e w r o n g c o m p o u n d s .


Organometallic Derivatives of Sucrose as Pesticides RC POLLER and

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