Porphyric Pesticides - ACS Publications - American Chemical Society

Chapter 3

Synthesis of Protoporphyrinogen Oxidase Inhibitors Robert D . Clark

Downloaded by EMORY UNIV on January 27, 2016 | http://pubs.acs.org Publication Date: April 15, 1994 | doi: 10.1021/bk-1994-0559.ch003

Monsanto Company, 800 North Lindbergh Boulevard, St. Louis, M O 63167

A n overview of general synthetic approaches to inhibit ors of protoporphyrinogen oxidase i s presented. Cate gories covered i n c l u d e d i p h e n y l a n d pyrazole nitrophenyl ethers; pyridone carboxanilides; phenyl uracils and carbamates; C - a n d N-phenyl pyrazoles; N-phenyl cyclic imides; oxadiazon; triazinediones; tetrazolones; and triazolidinone herbicides.

A n exhaustive review of the enormous range of literature covered b y the title i s far beyond the scope of this paper. Instead, a n effort i s made to touch on general synthetic routes for herbicide classes discussed by other contributors to this symposium, while including those specific examples most often cited w i t h i n each class as end-products. Acifluorfen a n d oxyfluorfen, for instance, were taken as archetypal diphenyl ethers. S u c h common names are used where possible to facilitate cross-reference w i t h the biochemical a n d physiological literatures. T o the same end, more arbitrary serial designations {e.g., DLH-1777) are alluded to where they have been published. E a r l y preparative steps have been generalized as m u c h as possible, i n the hope of providing information useful for synthesis of analogs for studying quantitative structure/activity relationships (QSAR). Because of space limitations, references are not necessarily to earliest publications. A conscious effort was made to preferentially cite literature w h i c h includes experimental details specific to archetypal examples of each class while at the same time m a i n t a i n i n g generality. F o r ease of general access, reports from refereed journals a n d U n i t e d States patents have been cited where available. I n addition, more efficient synthetic methods are cited i n most cases to the exclusion of less efficient methods published earlier.

0097-6156/94/0559-0034$08.00/0 © 1994 American Chemical Society

In Porphyric Pesticides; Duke, Stephen O., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.

3. CLARK

Synthesis of Protoporphyrinogen Oxidase Inhibitors

35

Organization M o s t i f not a l l protoporphyrinogen oxidase (Protox) inhibitors w h i c h have been identified to date are comprised of a n a r y l r i n g l i n k e d to some other cyclic functionality, w h i c h may or may not itself be aromatic. The different bridging groups involved provide a convenient way to organize a discussion of the synthetic methods used i n preparation of the various classes. O-Bridged inhibitors include a r y l nitrophenyl ethers such as acifluorfen, oxyfluorfen and pyrazole phenyl ethers, as well as phenyl carbamates such as phenopylate. F o r purposes of discussion, C-linked inhibitors are taken here to include a l l ketoaryl derivatives, encom passing pyridones such as D L H - 1 7 7 7 as well as C - p h e n y l pyrazoles. There are so many distinct classes of iV-linked Protox inhibitors that i t is useful to distinguish anilide derivatives from those prepared from phenyl hydrazines. The former group includes the iV-phenyl uracils (e.g., U C C - C 4 2 4 3 ) a n d iV-phenyl cyclic i m i d e s such as c h l o r o p h t h a l i m , S 23142 and K S 307829. Hydrazine derivatives include oxadiazon and iV-aryl pyrazoles such as T N P P - E t h y l a n d M & K 39279, as w e l l as t r i azinediones, tetrazolones and triazolidinones (e.g., F6285).


3

I H \ ) O-Bridged

*

(

L y

C-Linked

Anilide derivative

Hydrazine derivative

O-Bridged Inhibitors Diphenyl ethers. The central reaction of nitrodiphenyl ether synthesis is generally coupling of a phenolate anion w i t h a halophenyl r i n g acti vated toward aromatic nucleophilic substitution. Fluorodifen (1) a n d other 2,4-dinitrophenylethers are readily prepared i n this way (1).

S u c h direct syntheses require rather h a r s h conditions and do not work well for less activated substrates such as 3,4-dichlorobenzotrifluorides, nor for more w e a k l y nucleophilic phenols such as 5-hydroxy-2-nitrobenzoate. A more general approach is to condense a phenolate salt 2 w i t h a n a r y l halide and nitrate afterwards i n m i x e d acids, w i t h acetic


36

PORPHYRIC PESTICIDES


anhydride often being a useful co-solvent. Somewhat surprisingly, the latter reaction is usually quite regiospecific, giving the para nitrophenyl ether 3 as the major or exclusive product. Often a n intermediate trans formation of phenyl substituent Z (e.g., a l k y l a t i o n of a phenol or carboxylate) is involved. Chlorination and other electrophilic substitutions can also be carried out at the 4' position (2).

2

3a:Z = H 3b : Z = OCHMeCO>R 3c:Z = C0 R 2

2

2

Adducts such as 3 may themselves be products of interest, as i s the case for nitrofluorfen (3a) (3), acifluorfens (3c) (4,5), or lactate ethers (3b) (6). More often, they serve as substrates activated toward subse quent aromatic nucleophilic substitution. T h i s tactic is general, a n d par t i c u l a r l y useful for synthesis of 3'-polyethers such as 5 from sodium alkoxyethanolates (7) (an unusual example i n which the 4-substituent is a trifluoromethoxy group). The simplest method entails exhaustive a r y l a t i o n of resorcinol, followed by n i t r a t i o n to a n adduct such as 4. Note that symmetry of substitution effectively increases the regiospecificity of n i t r a t i o n , and that subsequent phenolate displacement takes place almost exclusively ortho to the nitro group. T h i s route i s h i g h l y advantageous for large-scale syntheses where chromatographic separa tions m a y be impractical. Note, too, that 5 and analogous compounds cannot be obtained by direct alkylation of (nitro)phenolic intermediates.

F CO 3


3. CLARK

37


T r i a r y l diether 3d has also been used i n the preparation of oxyfluorfen (6a) (3,8,9), as has the 3'-fluoro 3e. U n l i k e the diether, the fluoride can be converted to 3'-thioethers 6b as well (10). The 3\4'-dinitrophenyl ether 3f , prepared from m-nitrophenol, is even more versatile i n that i t can readily react w i t h amines to form 6c (11). FX, O' 3 d : Z = OAr v.7"Mn jr.Z-NU

6 a : Y R = OEt 6 b : Y R = SR 6c: Y R = NHR


2

Introducing either a n amino or a thioether functionality before nitration would l i k e l y lead to oxidation by-products. The broader applicability of 3-fluoro 3e m a y be offset, however, by reduced regiospecificity of nitra tion. The reported yield of 3'-nitro 3f , on the other hand, is 91% (11). C h i r a l lactate diphenyl ethers 6e (RH-4638) and 6f (RH-4639) can be prepared from the tosylates of ethyl (S)- and (U)-lactate, respectively, and potassium phenolate 6d w i t h clean inversion at the a-carbon (12). F ^ 6d + yt (YR = OK) Ts0"X0 Et 2

^

JC\

^

^N0

2

* McCN 1

2

6f:R =Me,R =H 5-Trifluoromethyl-2-pyridyl nitrophenyl ethers can also be prepared by displacement of chloride from precursors w i t h phenolates (13). Pyrazole nitrophenyl ethers, i n contrast to the u s u a l case for d i phenyl ethers, are synthesized from 4-halonitrobenzenes a n d 3-hydroxypyrazole 8. The latter is prepared by reaction of the enamine 7a or the enol ether 7b of ethyl trifluoroacetoacetate w i t h methyl hydrazine (14), followed by chlorination w i t h l,3-dichloro-5,5-dimethylhydantoin.

9

Me2S0

3

4

Y

R

l)MeNHNH

7a: Y R = OMe 7b: Y R = N H

F 3 C 2

\L=/

C I

MeCN 8

2

Direct condensation of trifluoroacetoacetate w i t h methylhydrazine yields p r i m a r i l y (15) the 5-hydroxy pyrazole isomer, nitrophenyl ethers of w h i c h are much less potent herbicides (16). The 5-hydroxy isomer is a


38



minor component i n preparations from enol ether 7a or enamine 7b, but is easily removed since its m u c h higher acidity renders i t soluble i n bicarbonate. Hydroxypyrazole 8 can also be prepared from 4,4,4-trifluorobutynoate esters (17); methods for synthesizing other hydroxypyrazoles, including 5-methanesulfonyl analogs, are given i n detail elsewhere (18). 2-Heterosubstituted nitrobenzenes 9b-c may be prepared from 2,4-difluoronitrobenzene and subsequently coupled w i t h hydroxypyrazole 8 to yield the respective 3-amino, -alkoxy or -thioether products 10(18,19); the 3'-unsubstituted 10a is A H 2.430 (16).

X

8

9a:X %:X 9c: X 9d:X

=F,Z= H = F , Z = OR = F, Z = N R * R = Cl,Z = C0 R 2

2

10a:Z 10b:Z 10c: Z lOd: Z

=H = OR = NR*R = C0 R

2

2

The nitrobenzoate 9 d is activated enough to undergo reaction as a n a r y l chloride to afford the acifluorfen analog A H 2.431 (lOd, R = H ) , which is only very weakly herbicidal (16). I n cases such as 10a and lOd, where the nitrophenyl r i n g i n the product is not too activated towards electrophilic attack, i t may be better to chlorinate the pyrazole r i n g after formation of the pyrazole phenyl ether rather t h a n before coupling has been carried out. C h i r a l iV-pyrazoloxyphenyl amino acids l O f are readily synthesized from the 3'-fluoro l O e w i t h excellent retention of configuration by u s i n g catalytic copper fluoride i n JV-methylpyrrolidinone ( N M P ) (12). Conver sion to the corresponding amides lOg-h ( A H 4.441 a n d A H 4.442, re spectively) is by way of the mixed anhydrides. HN

C0 Et catCuF

2

2

1

R* R

2

2

KoCCh A

COOH lJClCO^iBu TEA THF 2) M e N H

2

l O g : R ^ H , R =iPr

2

lOh.-R'affir.R^H CONHMe


3. CLARK


39

P h e n y l carbamates, like 3'-alkoxy diphenyl ethers, are prepared from halophenols or haloresorcinols. Phenopylate (11a), for instance, i s made by reaction of 2,4-dichlorophenol w i t h a carbamoyl chloride (20); the latter i s made using phosgene. A l t h o u g h 5'-substituted analogs such as R H 0978 ( l i b ) can also be prepared this w a y 81), a n alternative route (22) u s i n g trichloromethyl chloroformate ( D i p h o s g e n e ® ) i s to be pre ferred on a laboratory scale.

J^N-COCI

ONa


M^CO or ^ 2

1) ClCOzCCk H 0 2

2

n

>YC "

h

lla:Y=CH ,Z=H l i b : Y=CF , Z = O C H f e C H 2

2

Et 0

2

2

C-Bridged Inhibitors C - A r y l pyrazoles fall into two synthetic categories distinguished by the first steps i n their respective syntheses. The 5-alkoxy compounds 13 are derived from benzoylacetates 11 formed by condensation of dihaloacetophenones w i t h diethyl carbonate (23). Methylhydrazine reacts w i t h 11 to afford hydroxyarylpyrazoles, which can then be alkylated and halo genated to give, for example, 12a. Intervening reaction w i t h Lawesson's reagent yields thioethers such as 12b.

C0 Et 2

1) M e N H N H

2

2) (Lawesson's reagent) 3) F CHC1 base 2

2

4^ IX - Rr r i l

4) [X - B r , C l ]

+

1

2

a

1 2 b

:

=

0 C F

2H

: Y R = SCFoH

F u r t h e r elaboration can be accomplished by electrophilic substitution


40



of the phenyl ring, followed by reduction and alkylation, typically w i t h propargyl bromide or w i t h a bromopropionate ester. T h u s , chlorosulfonylation leads to thioethers 13a, whereas alkoxy analogs 13b re quire a moderately efficient (46% yield) diazotization step following nitration and reduction.

3-Phenyl-5-fluoroalkyl analogs 16 are synthesized by a rather differ ent route beginning w i t h 2,5-difluoroacetophenone 14 (24). The product is condensed w i t h trifluoroacetate, then w i t h hydrazine. A l k y l a t i o n and chlorination give the desired 3-phenylpyrazole isomer 15.

N i t r a t i o n allows heterosubstituents to be introduced at the 5'-position by nucleophilic aromatic substitution u t i l i z i n g catalytic copper fluoride i n AT-methylpyrrolidinone. Reduction w i t h elemental i r o n followed b y Sandmeyer diazonium chemistry yields the target compounds 16a-c.


3. CLARK

Synthesis of Protoporphyrinogen Oxidase Inhibitors CF

1) H N 0 H S0 15

4

1

2) Y R NMP Y

K2CO3

cat C u F

3

1) Fe AcOH

3

2

41

16a:Y = 0 16b:Y = S 16c: Y = N R

2) CuCl tBuONO RI MeCN

YR

2

1

2


f

5 -Alkoxy analogs such as propargyl ethers are not directly accessible b y this route. A s a n alternative, methoxy precursors (16a, Y R = O M e ) can be cleaved w i t h boron tribromide i n methylene chloride, a n d the phenols obtained reacted w i t h alkylbromide i n dimethylformamide (24). 1

P y r i d o n e carboxanilides are synthesized by condensation of a p r i m a r y amine w i t h a n acylacetanilide and enol lactone 17 to give the parent pyridone carboxanilide 18, w h i c h can be brominated regioseleotively at C on the pyridone ring, even when the pendant N substitu ent is a n electron-rich aryl (19a) (25). A m o n g the most active examples described to date is D L H - 1 7 7 7 (19b) (26). 6

1

18

1

19a: R = Me, R = CH CH Ph 19b:R =Pr,R =Me 2

2

1

2

2

Anilide derivatives Carbonylphenyl uracils. The published synthesis of these herbicides begins from isocyanate 21 (27), which can be prepared from aniline pre cursor 20. T h i s is condensed w i t h trifluoromethyl enamine 7b and alky lated to yield carboxyphenyl uracils 22.


42


NH x

NCO

2

l )

" Y i cico ca ^ v g ^ s , 2

7

b

N a H

3

CI

CI

2©

21

MejCO


22a:X = F 22b:X = H If a n ester other t h a n ethyl i s desired i n the final product, as i s the case for U C C - C 4 2 4 3 (22b where R = i P r ) , the ester m a y be introduced early i n the synthesis by acid-catalyzed transesterification of 20, or, later, by hydrolysis and re-esterification of 22. J V - P h e n y l i m i d e s are synthesized by reaction of substituted haloanilines 23 w i t h tetrahydrophthalic anhydride ( T H P A ) . M K 616 (24a), for example, i s prepared from the commercially available 4-chloroaniline (28).

x z A J

Acp

y « /

z 2

z

3

o 1

2

24a:X =Z=H,X =Cl Ub:X =¥ X =a Z=OR 24c:X =F,X =Cl,Z=OH l

2

9

9

1

2

M o r e potent herbicidal analogs require more h i g h l y functionalized anilines, however. To obtain fluoroalkoxy derivatives such as K S 307829 (24b, R=iPr), fluorohalophenol i s protected by acylation to carbonate 25, nitrated at C a n d then deprotected i n base. Nitrophenol 26 so obtained can then be alkylated and reduced to give 23b, a common intermediate key to synthesis of m a n y JV-phenyl azole herbicides. A l k o x y anilines 23b condense w i t h T H P A to yield imides 24b. 5

1)HN0 H S0

ClCO^Me aqNaOH

2

Y

3 4

2)aqNaOH A X OC0 Me

A y

N

° 2

> V ^

2

25

OH 26


3. CLARK

OR

OH

23b


43


23c

Nitrophenol 2 6 can also be reduced directly. The product aminophenol 2 3 c itself reacts cleanly w i t h T H P A to form the 5-hydroxyphenyl 2 4 c , w h i c h can then be alkylated. Published results suggest, however, that this alternative route gives a low overall yield (17% yield (29)). F o r those alkoxy substituents which m a y be sensitive to catalytic hydrogenation (e.g., S 23142 (24b, R=propargyl)), the latter route may s t i l l be the preferred one. The strategy outlined above i s restricted to those instances i n w h i c h substituent X i s strongly para-directing : syntheses of analogs bearing meta-directing substituents require major departures from that route, as does preparation of 4-unsubstituted imides (24, X = H ) . The imido acetophenone 27 can be prepared by reduction of the cor responding nitroactophenone and reaction w i t h T H P A . Conversion to the alkoxy analog 2 4 d is accomplished by a Baeyer-Villiger oxidation, followed by hydolysis and a l k y l a t i o n (30). Electrophilic substitutions and reduction then afford 24e-g. 4 -Nitro 2 4 f is the most active of these analogs (29). 2

2

f

2

0=C 1) C F 3 C O 3 H

24e: X = S R

>=0

1

N

2) H O MeOH Me 3) RBr

2

24f: X = N 0

2

2

24g: X = N H R 27

O

P h e n y l Hydrazine Derivatives There are several iV-aryl heterocycle classes of Protox i n h i b i t o r w h i c h are derived from phenyl hydrazines. These are, i n turn, prepared from various haloanilines b y diazotization a n d reduction w i t h stannous chloride. 1) N a N 0 aqHCl

2

2

3

29a: X = H , X =C1, Z=OR 29b: X =X =C1, X = C F , Z=H 29c: X*=H, X =X =Z=C1 29d: X =Z=H, X =C1 1

2

3

3

2) S n C l

2

2

2

3

3


44



JV-Aryl pyrazoles and oxadiazon. Acylation of 29a ( X ^ C l , R=iPr) w i t h trimethylacetyl chloride a n d reaction of the r e s u l t i n g hydrazide w i t h phosgene gives oxadiazon (30) (32). Condensation of phenylhydrazines w i t h ethoxyacrylonitriles yields 5-aminopyrazoles, i n c l u d i n g the Protox inhibitor M&B 39279 (31) from hydrazine 29b (32), whereas re action w i t h ethoxyacrylate esters affords 5-pyrazolones. N i t r a t i o n a n d a l k y l a t i o n of the pyrazolone derived from 29c produces T N P P - e t h y l (32) and analogous compounds (33). Note that although the p a r t i c u l a r herbicides cited are derived from specific hydrazines, the cyclization reactions are general. Subsequent transformations, however (such as regiospecific n i t r a t i o n of a n y iV-(alkoxyphenyl)pyrazole pre pared from 29a), might well be difficult to achieve i n particular cases.

l)EtO^^ ° C

J N

V *..A^

l)tBuCOa Ft-M

2

E

^N0

t

2

/r*/ Me N X - ^ ^ Q ^ ^C0 Et 2

2)

NO03 HN Acp/AcOH 3

N

2

3) BrCHMeCO^Et K C03 MeCOEt 2

1) EtOCH=C(CN) 2) E t O C H C H O H A

2

2

2

Triazinediones, tetrazolones a n d triazolidinones. Conversion of 29a to a hydrazone a n d subsequent reaction w i t h isocyanate a n d pyruvic acid gives triazinedione 33 (34), whereas reaction of 29 w i t h pyruvic acid and phosphoryl azide gives triazolidinones 34 (35,36).

Me,CO H2SO4 THF

1) M e C O C Q H aqHCl

29 2)KOCN 2) (PhO) P(0)N AcOH Et N 3) M e C O C Q H PhMe H S0 A dioxane 2

3

3

2

4


3.

CLARK


45

In a closely related reaction, tetrazolones 35 are formed from substi tuted anilines and trimethylsilyl azide (37).

1) C I C O ^ PhMe A


Z

2) Me3SiN A

3

A l l three classes of c h e m i s t r y m u s t be iV-alkylated to elicit full herbicidal activity. The most potent triazinediones (36a, Q=CMeC(0)) bear a n iV^-methyl group, whereas the most active tetrazolones (36a, Q=N) a n d triazolidinones (36a, Q = C M e ) bear N - fluoropropyl a n d difluoromethyl groups, respectively. 4

36a: Z=OR 36b: Z=H

[Q = CMe, N , orCMeC(O)]

2

The first two alkylation reactions proceed i n good yield, but the reaction of triazolidinone 34 w i t h Freon-22 (CF2HCI) i s problematic. Potassium hydroxide as base i n tetrahydrofuran, u s i n g phase transfer catalysis, gives a rather poor yield, and delaying that alkylation u n t i l later i n the synthetic sequence does not improve the situation (35). A subsequent publication (38) describes r u n n i n g this reaction w i t h potassium carbo nate as base i n dimethylformamide, but yields were not given. O - A l k y l a t i o n completes the synthesis for 5'-alkoxy herbicides (36a) (35). The more widely cited analogs, however, are 5'-sulfonamido ana logs such as triazolidinone F6285 (37a, X = C 1 , R = C H F , R = M e ) pre pared from 5'-unsubstituted 36b (36,38) by n i t r a t i o n , reduction a n d sulfonylation. 1

1

2

2

36b

1) H N 0 H SQ 2

3 2

4 >

2) Fe aqAcOH

R S0 C1 2

C H N " CH C1 5

5

2

37a: Q=CMe 37b: Q=N

2

NHS0 R

2

2


46


A n alternative preparation of tetrazolone 37b (X =F) by regioselective reduction of 2-fluoro-1,5-dinitrobenzene has also been reported (39); the chloro group is introduced subsequently by electrophilic substitution from sulfuryl chloride. 1

Acknowledgements


The Author wishes to thank Carl Hubenschmidt for indispensable bibliographic support. Kurt Moedritzer and Bruce C. Hamper provided access to key background literature. Along with James I. McLoughlin and Richard J . Anderson, they also provided helpful suggestions with regard to style and composition. Literature Cited 1. Martin, H . ; Aebi, H.; Ebner, L . U.S. Patent 3322525, 1967, Ciba Ltd. 2. Takahashi, R.; Fujikawa, K.; Yokomichi, I.; Toki, T.; Someya, S. U.S. Patent 3966453, 1976, Ishihara Sangyo Kaisha Ltd. 3. Yih, R.Y.; Swithenbank, C. J. Agric. Food Chem., 1975, 23, 592. 4. Johnson, W.O. U.S. Patent 4031131, 1977, Rohm and Haas Co. 5. Johnson, W.O.; Kollman, G . E . ; Swithenbank, C.; Y i h , R.Y. J. Agric. Food Chem. 1976, 26, 705. 6. Rohr, O.; Pissiotas, G.; Bohner, B. U.S. Patent 4221581, 1980, CibaGeigy Corporation. 7. Hiraga, K . ; Shibayama, S.; Yanai, I.; Harada, T. U.S. Patent 4226616, 1980, Nihon Nohyaku Company, Ltd. 8. Bayer, H.O.; Swithenbank, C.; Yih, R.P. U.S. Patent 4046798, 1977, Rohm and Haas Company. 9. Bayer, H.O.; Swithenbank, C.; Yih, R.Y. U.S. Patent 3798276, 1974. 10. Rohe, L . ; Schramm, J.; Klauke, E . ; Eue, L.; Schmidt, R.R. U.S. Patent 4104313, 1978, Bayer Aktiengesellschaft. 11. Yoshimoto, T.; Igarashi, K.; Oda, K.; Ura, M . ; Sato, N . U.S. Patent 4277624, 1981, Mitsui Toatsu Chemicals, Inc. 12. Nandihalli, U . J . ; Duke, M.V.; Ashmore, J.W.; Musco, V.A.; Clark, R.D.; Duke, S.O. Pestic. Sci., 1994, i n press 13. Nishiyama, R.; Fujikawa, K.; Haga, T.; Toki, T.; Komyoji, T.; Sakashita, N.; Maedea, K. U.S. Patent 4235621, 1980, Ishihara Sangyo Kaisha Ltd. 14. Gaede, B.J.; Torrence, L . L . U.S. Patent 4984902, 1990, Monsanto Company. 15. Lee, L.F.; Schleppnik, F . M . ; Schneider, R.W.; Campbell, J.W. J. Heterocyclic Chem., 1990, 27, 243. 16. Sherman, T.D.; Duke, M.V.; Clark, R.D.; Sanders, E.F.; Matsumoto, H . ; Duke, S.O. Pestic. Biochem. Physiol., 1991, 40, 236. 17. Hamper, B.C.; Kurtzweil, M.L.; Beck, J.P. J. Org. Chem., 1992, 57, 5680. 18. Moedritzer, K.; Allgood, S.G.; Charumilind, P.; Clark, R.D.; Gaede, B . J . ; Kurtzweil, M . L . ; Mischke, D.A.; Parlow, J.J.; Rogers, M.D.; Singh, R.K.; Stikes, G.L.; Webber, R.K. i n Synthesis and Chemistry of Agrochemicals III; Baker, D.R., Fenyes, J.G., Steffens, J . J . , Eds.; ACS Symposium Series No. 504; A C S Press: Washington,D.C., 1992; pp. 147-160. In Porphyric Pesticides; Duke, Stephen O., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.


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