ZA200604258B - Herbicidal pyrimidines - Google Patents

Description

TITLE

HERBICIDAL PYRIMIDINES

FIELD OF THE INVENTION

This invention relates to certain pyrimidines, their N—oxides, agriculturally suitable 5S salts and compositions, and methods of their use for controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely impeortant in achieving high crop efficiency. Achievement of selective control of the growtlm of weeds especially in such useful crops as rice, soybean, sugar beet, com (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecke d weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or'have different modes of action.

World Patent Application Publication WO 92/05159-A discloses pyrimidines useful as plant protectants, especially fungicides. European Patent Application Publication

EP-136976-A2 discloses pyrimidines as plant growth regulators. U.S. Patent 5,324,710 discloses sulfonated heterocyclic carboxamide derivatives of pyrimidines as herbicides and 2«@ growth regulators.

SUMMARY OF THE INVENTION

This invention is directed to a compound of Formula J including all geometric and stereoisomers, N-oxides or agriculturally suitable salts thereof, agricultural compositions containing them and their use as herbicides: 2

RS R4 | I wherein

R1 is cyclopropyl optionally substituted with 1-5 R53, isopropyl optionally substituted with 1-5 RS, or phenyl optionally substituted with 1-3 R7;

R2 is ((O);CRIIRIONR;

R is CO,H or a herbicidally effective derivative of COoF;

R3 is halogen, cyano, nitro, OR20, SR2! or N(R22)R23;

R4 is -N(R24)R? or -NOy; each RS and RS is independently halogen, C1—Cg alkyl, C;-Cg haloalkyl, C,—Cg alkenyl, C,—Cg haloalkenyl, C;—C3 allkoxy, C;—C, haloalkoxy, C;-Cj alkylthio or C;-C, haloalkylthio; each R7 is independently halogen, cyano, nitro, C;-C,4 alkyl, C1—Cq haloalkyl, C5;—Cg cycloalkyl, C3~Cg halocycloalkyl, Cy —Cy4 hydroxyalkyl, Co-Cy4 alkoxyalkyl,

C,-C4 haloalkoxyalkyl, C,—C alkenyl, C;—C4 haloalkenyl, C3-C4 alkynyl,

C3-C4 haloalkynyl, hydroxy, C;—Cy4 alkoxy, C;—C4 haloalkoxy, C;-Cy alkenyloxy, C,—C haloalkenyloxy, C3—-Cy alkynyloxy, C3~C4 haloalkynyloxy,

C,—C, alkylthio, C;~Cy4 haloalkylthic, C;~C, alkylsulfinyl, C;—C4 haloalkylsulfinyl, C;~Cy alkylsulfony/1, C;—C, haloalkylsulfonyl, C,-Cy4 alkenylthio, C,—C,4 haloalkenylthio, Cy—Cj alkenylsulfinyl, Co-C4 haloalkenylsulfinyl, C,—C alkenylsudfonyl, C,—C,4 haloalkenylsulfonyl, C3-Cy4 alkynylthio, C3~Cy4 haloalkynylthio, C3—Cy4 alkynylsulfinyl, C3-C4 haloalkynylsulfinyl, C3—C4 alkynylsulfonyl, C3~C4 haloalkynylsulfonyl, C;—C4 alkylamino, C,—Cg dialkylamino, C3—Cg cycloalkylamino, C4—Cg (alkyl)cycloalkylamino, Cy—Cg alkylcarbonyl, C,—Cg alkoxycarbonyl, C;—Cg : alkylaminocarbonyl, C3—Cg dialkylarninocarbonyl,-C3—Cg trialkylsilyl, phenyl, phenoxy and 5- or 6-membered heteroaromatic rings, each phenyl, phenoxy and : 5- or 6-membered heteroaromatic ring optionally substituted with one to three substituents independently selected from R45; or two adjacent R7 are taken together as -OCH,,0-, -CH,CH,0-, -OCH(CH;)0-, -OC(CH3),0-, -OCF,0-, -CF,CF,0—, -OCF,CF,0- or -CH=CH-CH=CH-;

R15 is H, halogen, C;—Cy alkyl, C;~Cy4 haloalkyl, hydroxy, C;—Cj alkoxy or CC, alkylcarbonyloxy;

R16 is H, halogen, C;—C4 alkyl or C;—C4 haloalkyl; or

R15 and R16 are taken together as an oxygem atom to form, with the carbon atom to which they are attached, a carbonyl moiety; :

R20 ig H, C;~C, alkyl or C;~Cj haloalkyl;

R21 is H, C;-C4 alkyl or C;—Cj haloalkyl;

R22 and R23 are independently H or C;—C4 alkyl;

R24 is H, C;~C4 alkyl optionally substituted] with 1-2 R30, C,—C, alkenyl optionally substituted with 1-2 R31, or C,—C4 al kynyl optionally substituted with 1-2 R32; or R24 is C(=O)R33, nitro, OR34, S(O)R35, N(RIOR37 or N=C(R62)R63;

R25 is H, C;-C, alkyl optionally substitutec] with 1-2 R30 or C(=0)R33; or

R24 and R25 are taken together as a radical selected from -(CHp)4-, (CHp)s-, -CH,CH=CHCH,- and -(CH,),O(CHI,),-, each radical optionally substituted with 1-2 R38; or

R24 and R25 are taken together as =C(RIF) NR4OR4! or =C(R42)OR43; each R30, R3! and R32 is independently hal ogen, C{—Cj alkoxy, C;—C3 haloalkoxy,

C1C3 alkylthio, C1—C3 haloalkylthio, amino, Ci—C5 alkylamino, Cr-Cy dialkylamino or C,—C,4 alkoxycarbomyl; each R33 is independently H, C;—C 4 alkyl , C;~Cs haloalkyl, C,~C, alkoxy, phenyl, phenoxy or benzyloxy,;

R34 is H, C;—C, alkyl, C~C haloalkyl or CHRSSC(O)ORS’;

R35 is C;—Cy4 alkyl or C;—Cj haloalkyl;

R36 is H, C;—C, alkyl or C(=O)R%;

R37 is H or C;-C, alkyl; each R38 is independently halogen, C;—C3 alkyl, C;-Cj3 alkoxy, C{~Cj haloalkoxy,

C,-C; alkylthio, C;-Cj haloalkylthie, amino, C;~Cj alkylamino, C2~Cy dialkylamino or C,—C, alkoxycarbormyl;

R39 is H or C,—C4 alkyl;

R40 and R#! are independently H or C;—C.g alkyl; or

R40 and R4! are taken together as -(CHy)4—, -(CH3)s-, -CHyCH=CHCH,- or h + -(CHp)O(CHp),-; = "R42 is H or C1—C,4 alkyl; : . "R#is C;—Cy alkyl; SE 2 each R45 is independently halogen, cyano, nitro, C;—Cj alkyl, C;-C,4 haloalkyl, C3-Cg cycloalkyl, C3—Cg halocycloalkyl, C»-Cy alkenyl, C;-Cy haloalkenyl, C3-Cy alkynyl, C3—C4 haloalkynyl, C;—C4 alkoxy, C;-C4 haloalkoxy, C;-Cy4 alkylthio,

C;—C4 haloalkylthio, C;—Cy4 alkylsul finyl, C;—C, alkylsulfonyl, Ci—Cy alkylamino, C,—Cjg dialkylamino, C3.—Cg cycloalkylamino, C4~Cg (alkyl)cycloalkylamino, CoC alkyl carbonyl, C;—Cg alkoxycarbonyl, Cy—Cg alkylaminocarbonyl, C3—Cg dialkylacminocarbonyl or C3—Cg trialkylsilyl;

R62 js H, C;—Cj alkyl or phenyl optionally substituted with 1-3 R65;

R63 is H or C;-C4 alkyl; or

R62 and R63 are taken together as -(CHy)4— or -(CHp)s-;

R% is H, C;—-C4 alkyl, C;-Cj3 haloalkyl, €;—C4 alkoxy, phenyl, phenoxy or benzyloxy, each R65 is independently CH3, Cl or OCH;

R66 is H, C,—C, alkyl or C;-C, alkoxy;

R67 is H, C;—Cj4 alkyl or benzyl; jisOorl; and kisOorl; provided that: (a) when kis 0, then jis 0;

(b) when R2 is CH,OR®? wherein Re is H, optionally substituted alkyl or benzyl, then

R3 is other than cyano; (c) when R1is phenyl substitutated by Cl in each of the meta positions, the phenyl is also substituted by R7 in tke para position; (d) when R! is phenyl substittated by R7 in the para position, said R7 is other than tert-butyl, cyano or optiomally substituted phenyl; (e) when RI is cyclopropyl or" isopropyl optionally substituted with 1-5 RS, then R is other than C(=W)NRP)S(CO),-R¢-Rd wherein W is O, S, NR® or NOR®; Rbis hydrogen, C;—C4 alkyl, Co-Cg alkenyl or C,—Cg alkynyl; R€ is a direct bond or

CHR, O, NR¢ or NOR®; R¢ is an optionally substituted heterocyclic or carbocyclic aromatic radical having 5 to 6 ring atoms, the radical being optionally condensed with an aromatic or nonar<matic 5- or 6-membered ring; each Re is independently

H, C;—C; alkyl, C1~C3 haloalkyl or phenyl; and Rfis H, C{-Cj alkyl! or phenyl; and (f) the compound of Formula is other than diethyl 6-amino-3-nitro-2-phenyl- 4-pyrimidinemalonate. :

More particularly, this inven tion pertains to a compound of Formula I, including all geometric and stereoisomers, N-oxi des or agriculturally suitable salts thereof. This invention also relates to a herbicidal composition comprising a herbicidally effective amount of a: compound of Formula I and at least one of a surfactant, a solid diluent or a liquid diluent.

This invention further relates to a rmethod for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount . of a compound of Formula I (e.g., 2s a composition described herein). This invention also relates to a herbicidal mixture comprising a herbicidally effective amount of a compound of 25 . Formula I and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener. This invention further relates to a herbicidal composition comprising a herbicidally effective amount of a compound of Formula I, an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener, and at least one of a surfactant, a solid diluent or a liquid diluent.

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thesreof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. } Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a cond.ition A or B is satisfied by any one of the following: A is true (or presesnt) and B is false (or not present), A is false (or n«ot present) and B is true (or present), and. both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. 5S occurrences) of the element or component. Therefore “a” or “ar” should be read to include one or at lea st one, and the singular word form of the element or component also includes the plural unMess the number is obviously meant to be singular.

In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthios” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-prop yl, i-propyl, or the different butyl, pentyl or hexyl issomers. “Alkenyl” includes -straight-chair or branched alkenes such as ethenyl, 1-propenyl, =-propenyl, and the different butenyl, pemmtenyl and hexenyl isomers. “Alkenyl” also imcludes polyenes such as 1,2-propadiemnyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethy-myl, 1-propynyl, 2-propynyl and the different buty/mnyl, pentynyl and hexynyl isomers. “A_lkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiyn yl. “Alkoxy” includes, for example, methosxy, ethoxy, n-propyloxy, “7. - isopropyloxy- and the different butoxy, pentoxy and hexylox=y isomers. :.“Alkoxyalkyl” ’ denotes alkosxy ‘substitution on alkyl. "Examples of “alkoxy~alkyl” ‘include: CH30CH,;" ©» vw. CH30CH3CH], . CH3CHyOCH, «and CH;CH,OCH,CH,: . “Alkenyloxy” includes: straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include ~ HyC=CHCHz0, (CH3)CH=CHCH,0 and CH;=CHCH,CH,O». “Alkynyloxy” includes straight-chaima or branched alkynyloxy moieties. Examples of “alkynyloxy” include

HC=CCH,O and CH3C=CCH,0. “Alkylthio” includes branche or straight-chain alkylthio moieties suck as methylthio, ethylthio, and the different propyl thio and butylthio isomers. “Alkylsulfinys1” includes both enantiomers of an alkylsulfirayl group. Examples of “alkylsulfiny®” include CH3S(0), CH3CH,S(0), CH;CH,CH,S(CO), (CH3),CHS(O) and the different bu-tylsulfinyl isomers. Examples of “alkylsulfonyl” include CHj3S(0),,

CH;CH»S(0D,, CH3CH;CHS(0)y, (CH3);CHS(0), and the different butylsulfonyl isomers. “Alkylamino”, “dialkylamino”, “alkenyl®hio”, “alkenylsulfinyl”, “alkenylsulfo myl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsu_lfonyl”, and the like, are defined anal ogously to the above examples. “Cycloalkyl ™ includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cyclowalkyl moieties bonded to straight-chain or branched alkyl groups. “Alkylcycloalkyl” deneotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-eethyicyclopentyl. The term “heteroaromactic ring” includes fully aromatic heterocycles. Arommatic indicates that each of the ring atom_s is essentially in the same plane and has a p-orbitzal perpendicular to the ring plane, and in which (4n + 2) 7 electrons, when n is 0 or a posi_tive integer, are associated with the ring to comply with Hiickel’s rule. The terrm carbocyclic aromatic radical is synonymous with the term isocyclic aromatic radical. A wide variety of synthetic methods are known in the art to enable preparation of aromatic heterocyclic rings; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of

Comprehensive Heterocyclic Chemistry II, A. R. Katritzkyz, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996. The 5— and 6-membered heteroaromatic rings described for R7 typically comprise 1 to 4 heteroatom ring members, the heteroatom members selected from 0-4 N, 0-1 O and 0-1 S atoms. Exhibit 1 shows examples of heteroaromatic rings; H-1 through H-55 are to be comstrued as illustrative rather than limiting of the heteroaromatic rings within the scope of thes present invention.

Exhibit 1 3 / : &p 4 4 3 4 71, 7» AX, , N ®7y

AZT LET A3" . RZ

H-1. : H-2 . H3 H-4 71 71 N

N ®R'%)y N Rg / OW ®"Y,

M ? M r 4 3 / ? 5 5 2 0 0 s”

HS H-6 H7 H-8 3 4 4 N 4 a 4 3 J / ®R7Yy 3 Yq 71 ’ 2 9 § 2 5 >»

AF o” 19:97) In R72

H-9 H-10 H-11 H-12

R712 3

N—N ’ N—N ’ ya Pa ’ J ’ [ 71 3 d

R a R’la (o) S R72 R72

H-13 B-14 H-15 H-16

Rr71a R12 rR} n— N N N

IEE s SR s TDs o” sg” o” R71a o”

H-17 H-18 H-19 H-20 ¢ 71 N 71 4 7 4 on d R% [| XR ff ®R Dp J ® Pp 2 5 NO 5 2 5 2 5 in : 3

H-21 H-22 H-23 H-24 ? 71 i Rg 3 ? N t 9 ] ®", J N &'h, J &", 5 2 5 py 5 y

R72 0 | $ S

H25 H26 H2T H28

I 71 [ Ce —( n—( [ a. ’ Pa N A pt 5 o” In r7ia 0” r7la 5”

H-20 H-30 H-31 H-32 4 — 2 __ 3 71 ) N , , 71 , “ =, Da W wml A 2 Pa s” R 5 x i” s

H-33 H-34 H-35 H-36 3 3 5 4 —=N

J Sam, , NG 2 ®7, , / A= ®h, ef, ~~ ~~ ’

Ns 5 0 5 5 3

H-37 H-38 H-39 H-40

A 4 4 3 5 5

N N = 71 Zz 71

A yy Oe Lr

NS

H-41 H-42 H-43 H-44 4 4 ZN x5 4 “Cx 34 &h, i En, Tr Fe :

Se 6 A 6 NZS

H-45 H-46 H-47 H-48 5 5 * = 377 RM : 6 “NP NF 3 2 X- 6 3 A

H-49 H-50 H-51 H-52 5 Asn 3 AN i

XN RT NT N 7 . Do 2 ZZ 6 NZ 6 NF 6

H-53 H-54 ' H-55 wherein each R7! is independently R45;

R71a, R72 and R73 are independently H or R43; p is an integer from 0 to 3; and 5 q is an integer from O to 2.

References herein to R7 groups H-1 through FI-55 refer to those shown in Exhibit 1.

One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair of electrons for oxidation to the oxide; one skilled in the art will recognize thos.e nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form

N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as #-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxiranee. These methods for the preparation of

N-oxides have been extensively described and reviewed in the literature, see for example:

T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S.V. Ley, Ed,

Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A.J. Boulton and A.. McKillop, Eds., Pergamon Press; M. R. Grimmett and B.R.T.Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky,

Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp285-291, A.R.Katritzky and A.J. Boulton, Eds., Academic Press; and

G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, . Pp 390-392, A. R. Katritzky and A_. J. Boulton, Eds., Academic Press.

The term “halogen”, either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F3C, CICH,, CF;CH, and

CF;CClp. The terms “haloalkeny®”, ‘‘haloalkynyl”, “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to time term “haloalkyl”. Examples of “haloalkenyl” include . (CH,C=CHCHj, and CF3;CH,CH=CHCH,. Examples of “haloalkynyl” include HC=CCHCI, + CF3C=C, CCI3C=C and FCH,C=CCH,. Examples of “haloalkoxy” includé¢! CF30, . CCI3CH,0, HCF,CH,;CH,0 and CF3CH,0. Examples of “haloalkylthio” include CCl;S,

CF;S, CClCH,S and CICH,CH,CH,S." Examples of “haloalkylsulfiny]” include CF3S(O),

CCIS(0), CFP3CH,S(0) and CF3CE,S(0). Examples of “haloalkylsulfonyl” "include

CF3S(0),, CCl38(0),, CF3CH,S(Q), and CF;CF,S(0),.

The total number of carbon atoms in a substituent group is indicated by the “C=C” prefix where i and j are numbers from 1 to 14. For example, C;~C5 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C, alkoxyalkyl designates CH3;0CH,; Cj alkoxyalkyl designates, for exampele, CH3CH(OCHj3), CH30CH,CH, or CH3CH,0CH,; and C, alkoxyalkyl designates the: various isomers of an alkyl group substituted with an alkoxy group containing a otal of fourcarbon atoms, examples including

CH3CH,CH,OCH,; and CH3CH5OCH,CH,. Examples of “alkylcarbonyl” include

C(O)CH3, C(O)CH,CHyCH3 and C(O)CH(CH3),. Examples of “alkoxycarbonyl” include

CH30C(=0), CH3CH,0C(=0), CH3CH,CH,0C(=0), (CH3),CHOC(=0) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of

Formula I is comprised of one or amore heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

When a compound is substitted with a substituent bearing a subscript (e.g., RY);_4) that indicates the number of instances (i.e. occurrences) of said substituent can vary or the substituent is preceded with a numeric range (e.g, 1-3 RY) indicating the number of instances of said subsituent can vary, then when the number of said instances is greater than

1, each instance is independently selected from thé group of radicals defined for the substituent. Further, when the subscript indicates a range, e.g., (R9);, then the number of substituent instances may be selescted from the integers between i and j inclusive. 0] 0 “-CH{C(O)O(CHp),,}’ mezans ; “-CH{O(CH,),}’ means Ths,

Co 0 CHyy

When a group contains a substituent which can be hydrogen, for example R15 or R34, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. oo

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoksomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formmulal, N-oxides and agriculturally . suitable salts thereof. The comapounds of the invention may be present as’ a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

The compounds of Formul a I wherein R is CO,H (i.e. a carboxylic acid function) are - believed to be the compounds &hat bind to an active site on a plant enzyme or receptor causing herbicidal effect on the plant. Other compounds of Formula I wherein the substituent R is a group that can be transformed within plants or the environment to a carboxylic acid function (i.e. CO,H) provide similar herbicidal effects and are within the scope of the present invention. Therefore “a herbicidally effective derivative of CO,H” when used to describe the substituent R in Formula I is defined as any salt, ester, carboxamide, acyl hydrazide, irmidate, thioimidate, amidine, acyl halide, acyl cyanide, acid anhydride, ether, acetal, orthoester, carboxaldehyde, oxime, hydrazone, thioacid, thioester, dithiolester, nitrile or any other carboxylic acid derivative known in the art which does not extinguish the herbicidal activity of the compound of Formula I and is or can be hydrolyzed, oxidized, reduced or otherwise metabolized in plants or soil to provide the carboxylic acid function, which depending upon pH, is in the dissociated or the undissociated form.

Agriculturally suitable salts of the compounds of the invention are salts formed by contact with acids or bases or through ion exchange such that the derived salts retain sufficient water solubility for bioavailability and thus herbicidal efficacy and that the counterions of the salts are suitab-le for use in agriculture. The agriculturally suitable salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric

~ acids. The agricwilturally suitable salts of the compounds of the invention also include those formed with strong bases (e.g., hydroxides of sodium, potassium, lithium or quaternary ammonium) or amines. One skilled in the art recognizes that because in thes environment and under physiological conditions salts of the compounds of the invention are in equilibrium with_ their corresponding nonsalt forms, agriculturally suitable s alts share the biological utility of the nonsalt forms.

Particularly. useful are agriculturally suitable salts of compounds of Formula I wherein

R is CO,H (incltading wherein RZ is CO,H) formed with strong bases or amines. As is well known in the =art, contact of a carboxylic acid group (CO,H) with a base causes deprotonation to give the corresponding carboxylate ion (CO,©) and a typically positively charged counterion derived from the base. An extensive range of coumterions form agriculturally sui table salts of compounds of Formula I wherein R is COoH, as most of the derived salts havee sufficient water solubility for bioavailability. Illustrative aned of particular note are salts of compounds of Formula I in which R is CO,H wherein the counterion ion is an alkali metal cation such as lithium, sodium or potassium, quarternary ammeonium such as tetramethylammonium, ternary sulfonium such as trimethylsulfonium, or demrived from an amine such as dimmethylamine, diethanolamine (diolamine), triethanolamine (tr-olamine).

Also particularly useful are ester and thioester derivatives of COE as R in the compounds of F-ormula I. As is well known in the art, ester groups (i.e. CCOO,RAL) result from condensatieon of a carboxylic acid fonction (CO,H) with an alcohol (i.e. RALOH) wherein RAL is the radical derived from the alcohol; a wide range of methods- are known to ~ prepare such esters. Analogously, thioester groups of formula C(O)SIRAL may be conceptually vieewed as the condensation product of a carboxylic acid fumction ‘with a thioalcohol (oftem called a mercaptan) of formula RALSH; a variety of methods are known to prepare such thicesters. As compounds of Formula X wherein R is COoH are herbicidally active and their clerived esters and thioesters are susceptible to hydrolysis (to R_ being CO,H) particularly in thee presence of hydrolytic enzymes, the compounds of Formula I wherein R1 is an ester (i.e. C ORAL) or thioester (i.e. C(O)SRAL) are generally useful as herbicides. Of the herbicidally effective derivatives of CO,H, the ester and thioester derivatives, particularly ester derivatives, are among the most conveniently prepared and useful. If the radical RAL has —more than one OH or SH function, the radical may then be condensed with more than one pyrimidine ring system of Formula I having CO,H as R. Aas the derived multiply esterified derivatives can be hydrolyzed to the compound of Forrmula I having

CO,H as R, said multiply esterified derivatives are among the herbicicRally effective derivatives of CCO,H. Illustrative and of note are ester and thioester compounds of Formula I in which R beirag CO,H is esterified with methanol, ethanol, butanol, 2-t>utoxyethanol, 2-ethylhexanol, i sopropanol, 2-methylpropanol (isobutanol), octanol isomers (Fsoctanol) and ethanethiol to form methyl, ethyl, butyl, 2-butoxyethyl, 2-ethylhexy.1, isopropyl,

2-methypropyl, isoctyl and ethylthio esters, respectively. Of particular notes are the methyl and ethyl esters.

Embodimeents of the present invention include:

Embodimerit 1. A compound of Formula I wherein j is 0.

Embodiment 2. A compound of Formula I wherein k is 0.

Embodiment 3. A compound of Formula I wherein R15 is H.

Embodiment 4. A compound of Embodiment 3 wherein R16 is H.

Embodiment 5. A compound of Formula I wherein

R is CO,RR12, CH,OR!3, CH(OR46)(OR47), CHO, C(=NOR!4)H, C(=INNR4R¥)H, - C(=0)NR!8R19, C(=S)OR30, C(=0)SR51, C(=8)SR52 or C(=N R33)YR34;

R12 js H, ~CHEC(O)O(CHy)}, -N=C(R35)R5S; or a radical selected from C-Cj4 alkyl, C3-Cj cycloalkyl, C4—C,, alkylcycloalkyl, C4—Ci; cycloalkylalkyl,

C,—C4 alkenyl, Co—C14 alkynyl and phenyl, each radical option ally substituted with 1-3 R?7; or

R12 is a divalent radical linking the carboxylic ester function CO,R12 oof each of two pyrimidine ring systems of Formula I, the divalent radical selected from -CHs-, (CE, «(CH,)s- and -CH(CH3)CH,-; =

R13 is H, CC alkyl optionally substituted with 1-3 R28, or benzyl;

Rl4 is H, C,-C, alkyl, C1—C, haloalkyl or benzyl; co So

RI8js H, C,—Cy alkyl, hydroxy, C;-C4 alkoxy or S(O),R57;

R19is H or C,-C, alkyl; each R27 His independently halogen, cyano, hydroxycarbonyl, C,—Cy4 alkoxycarbonyl, hydroxy, €;—C; alkoxy, C;—C, haloalkoxy, C1—C4 alkylthio, Cy —C4 haloalkylthio, amino, C,—Cy4 alkylamino, C,—C4 dialkylamino, -€CHFO(CHj),} or phemyl optionally substituted with 1-3 R44; or two R27 are taken together as -OC(O)O- or -O(CR38)(R58));_,0-; or two R27 are taken together as an oxygen atom to form, with the carborm atom to which they are attached, a carbonyl moiety; each R28 js independently halogen, C;~C, alkoxy, C1-C,4 haloalkoxy, C,—Cy4 alksylthio, C;~C4 haloalkylthio, amino, C;-C4 alkylamino or C;—C4 dial kylamino; or two R28 are taken together as an oxygen atom to form, with the carbora atom to which they are attached, a carbonyl moiety, each R44 is independently halogen, C;—C, alkyl, C;—Cj haloalkyl, hyciroxy, C;—C, alkoxy, C;—C3 haloalkoxy, C;—~Cj alkylthio, C;—Cj haloalkylthi ©, amino, C,—C; alksylamino, C,—C4 dialkylamino or nitro;

R46 and R47 are independently C,—C; alkyl or C;—Cj; haloalkyl; or

R46 and R47 are taken together as -CHyCHj~, -CH-,CH(CH3)- or (CHp)3-;

R48 is H, C;—-C, alkyl, C;—C, haloalkyl, C;~C,4 alkylcarbonyl, C2-C4 alkoxycarbonyl or benzyl;

R4¥ is H, C;—C, alkyl or C|~C, haloalkyl;

R30, R51 and R52 are H; or a radical selected from C;—Cj4 alkyl, C3-C); cycloalkyl,

C4—C,, alkylcycloalkyl, C4—Cis cycloalkylalkyl, C,—Cy4 alkenyl and Co~Cy4 alkynyl, each radical optionally substituted with 1-3 R27;

Y is O, S or NR6I;

R53 is H, C;~C; alkyl, CC; haloalkyl, C,~Cj alkoxyalkyl, OH or C;-Cj alkoxy;

R54 is CC; alkyl, C;~Cj haloalkyl or Cy—C, alkoxyalkyl; or

R53 and R54 are taken together as -(CHy),-, -CHyCH(CH3)- or -(CHy)s-

R55 and R36 are independently C1-Cy alkyl;

R57 is C;-C, alkyl, C;~C haloalkyl or NRSIRSO; each R38 is independently selected from H and C,—C; alkyl;

R59 and R60 are independently H or C;—C, alkyl;

R6! is H, C;~C; alkyl, C;—C5 haloalkyl or C,-C4 alkoxyalkyl; . mis an integer from 2 to 3; and CL

Co n is an integer from 1 to 4. ) : : Co

Embodiment 6. A compound of Formula I wherein when R1 is optionally substituted cyclopropyl, then R? is other than alkoxyalkyl or alkylthicalkyl.

Embodiment 7. A compound of Formula I wherein R2 is other than alkoxyalkyl or alkylthioalkyl.

Embodiment 8. A compound of Embodiment 5 whesrein

R2 is CO,R12, CH,ORI13, CH(OR46)(OR47), CHO, C(=NOR 4)H, C(=NNR48R4%)H, (O}CRISRI6ICORI7, CEONRIERL, C(=S)ORSO, C(=0)SRSY,

C(=S)SR32 or C(=NR33)YR4;

R17 js C;-C¢ alkyl optionally substituted with 1—3 R29, or benzyl; and each R29 is independently halogen, Cy—C, alkoxy, C;—C4 haloalkoxy, C1-Cy alkylthio, C;~C4 haloalkylthio, amino, C,—C4 alkylamino or C;—-C4 dialkylamino.

Embodiment 9. A compound of Embodiment 8 wherein when R3 is CH;OR!13, then R13 is other than alkyl.

Embodiment 10. A compound of Embodiment 8 wherein when R3 is CHyOR13, then

R13 js other than optionally substituted alkyl .

Embodiment 11. A compound of Embodiment 8 wherein R3 is other than CH;ORI13.

Embodiment 12. A compound of Embodiment 8 wkaerein j is O.

Embodiment 13. A compound of Embodiment 12 wherein R2 is CO,R12, CH,0R13,

CHO or CH,CO,R1!7.

Embodiment 14. A compound of Embodiment 13 wherein R? is CO;R12.

Embodiment 15. A compound of Embodiment 14 wherein R12 is H, C;—Cg alkyl or

C, alkyl substituted with phenyl optionally substituted with 1-3 R44.

Embodiment 16. A compound of Embodiment 15 wherein R12 is H, CC, alkyl or

C; alkyl substituted with phenyl optionally substituted with 1-3 R44,

Embodiment 17. A compound of Embodiment 16 wherein R12 is H, C;—C4 alkyl or benzyl.

Embodiment 18. A compound of Formula I whaerein R? is CO,H, an agriculturally suitable salt or an ester or thioester derivative thereof.

Embodiment 19. A compound of Embodiment 18 wherein R2 is COoH, an agriculturally suitable salt or an ester dexrivative thereof. :

Embodiment 20. A compound of Formula I whaerein R! is cyclopropyl optionally substituted with 1-5 RS.

Embodiment 21. A compound of Formula I wherein R1 is isopropyl optionally substituted with 1-5 RS. .

Embodiment 22. A compound of Formula I wherein R! is phenyl optionally substituted : with 1-3 R7. : :

Embodiment 23. A compound of Formula I wherein R! is cyclopropyl optionally substituted with 1-5 RS or isopropyl optionally substituted with 1-5 RS.

Embodiment 24. A compound of Formula I wherein R! is cyclopropyl optionally substituted with 1-5 RS or phenyl optionally substituted with 1-3 R7.

Embodiment 25. A compound of Formula I wherein R! is isopropyl optionally substituted with 1-5 R6 or phenyl optiorally substituted with 1-3 R7.

Embodiment 26. A compound of Formula I wherein R! is other than cyclopropyl.

Embodiment 27. A compound of Formula I wherein R! is cyclopropyl optionally substituted with 1-2 R6 or phenyl optionally substituted with 1-3 R7.

Embodiment 28. A compound of Embodiment 27 wherein R! is cyclopropyl optionally substituted with 1-2 RS.

Embodiment 29. A compound of Embodiment 27 wherein R! is cyclopropyl or phenyl optionally substituted with 1-3 R7.

Embodiment 30. A compound of Embodiment 28 wherein R! is cyclopropyl.

Embodiment 31. A compound of Embodiment 27 wherein R1 is phenyl} optionally substituted with 1-3 R7.

Embodiment 32. A compound of Embodiment 27 wherein R1 is cyclopropyl or phenyl substituted with a R7 radical in the para position and optionally with 1-2 R7 in other positions.

Embodiment 33. A compound of Embodiment 32 wherein R1 is cyclopropyl or phenyl substituted with a halogen, methyl or methoxy radical in the para position and optionally with 1-2 radicals selected from halogen and methyl in other positions.

Embodiment 34. A compound of Embodiment 33 wherein R! is cyclopropyl or phenyl substituted with a halogen radical in the para position and optionally with 1-2 radicals selected from: halogen and methyl in other positions.

Embodiment 35. A compound of Embodiment 34 wherein R1 is cyclopropyl or phenyl substituted with a Br or Cl radical in the para position and optionally with 1-2 radicals selected frome halogen and methyl in other positions.

Embodiment 36. A compound of Embodiment 35 wherein R1 is phenyl substituted with a Br or Cl radical in the para position and optionally with 1-2 radicals selected from halogen and methyl in other positions.

Embodiment 37. A compound of Embodiment 35 wherein R! is cyclopropyl or phenyl substituted with a Br or Cl radical in the para position.

Embodiment 38. A compound of Embodiment 37 wherein R! is phenyl substituted with a Br or Cl radical in the para position.

Embodiment 39. A compound of Formula I wherein R7 is other than cyano. ;

Embodiment 40. A compound of Formula I wherein R7 selected from other than optionally substituted phenyl, phenoxy and 5- and 6-membered heteroaromatic : rings. : : : Embodiment 41. A compound of Formula I wherein each R7 is independently selected from halogen, C;—C, alkyl, C;—C; haloalkyl, C;—C; alkoxy or C,-C, haloalkoxyj; or two adjacent R7 are taken together as. -OCH,0-, -CH,CH,0-, -OCH(CH3)0-, -OC(CHj3),0-, -OCF,0-, -CF,CF,0-, -OCF,CF,0- or -CH=CH-CH=CH-.

Embodiment 42. A compound of Embodiment 41 wherein each R7 is independently selected from halogen, C;-C; alkyl, C;—C; haloalkyl, C;-C; alkoxy or C;-C, haloalkoxy; or two adjacent R7 are taken together as -OCH,0-, -CH,CH;0-, -OCH(CH3)O- or -OCF,0-.

Embodiment 43. A compound of Embodiment 42 wherein each R7 is independently selected from halogen, C1-C, alkyl, C; fluoroalkyl, C;-C; alkoxy or

C fluoroalkoxy.

Embodiment 44. A compound of Formula I wherein each R7 is independently selected from halogen, methyl and methoxy.

Embodiment 45. A compound of Embodiment 44 wherein each R7 is independently selected from halogen and methyl.

Embodiment 46. A compound of Embodiment 45 wherein each R7 is independently selected from F, Cl arad Br.

Embodiment 47. A compound of Embodiment 46 wherein each R7 is independentlsy selected from Cl and Br.

Embodiment 48. A compound of Formula I wherein R3 is other than cyano.

Embodiment 49. A compound of Formula I wherein R3 is other than nitro.

Embodiment 50. A compound of Formula I wherein R3 is halogen, nitro, OR20, SRR?! or N(R22)R23.

Embodiment 51. A compound of Embodiment 50 wherein R3 is halogen.

Embodiment 52. A compound of Embodiment 51 wherein R3 is Br or CL

Embodiment 53. A compound of Embodiment 52 wherein R3 is Cl.

Embodiment 54. A compound of Formula I wherein R4 is -N(R?)R?>.

Embodiment 55. A compound of Formula I wherein R24 js other than C,—C,4 alkymmyl optionally sub stituted with 1-2 R32,

Embodiment 56. A compound of Formula I wherein R24 is H, C(O)R33 or C1-C4 alkyl optionally sub stituted with R30; R25 is H or C;-C; alkyl; or R24 and R% are taken together as =C(R39)N(R40)R41,

Embodiment 57. A compound of Embodiment 56 wherein R24 is H, C(O)CHj; or

C;~C; alkyl optionally substituted with R30; and R25 js H or C;-C, alkyl. :

I. Embodiment 58. A compound of Embodiment 57 wherein R%* and R25 are : independently H or methyl. ~~~ :

Embodiment 59. A compound of Embodiment 58 wherein R24 and R25 are H.

Embodiment 60. A compound of Formula I wherein R30 is halogen, methoxy,

C, fluoroalkoxy, methylthio, Cy fluoroalkylthio, amino, methylamino, : dimethylamin© or methoxycarbonyl.

Embodiment 61. A compound of Formula I wherein R33 is H or C;~C3 alkyl.

Embodiment 62. A compound of Embodiment 61 wherein R33 is CH3.

Embodiment 63. A compound of Formula I wherein R39 is H or C;-C, alkyl.

Embodiment 64. A compound of Formula I wherein R40 and R*! are independent] y H or C=C, alkyl.

Embodiment 65. A compound of Formula I wherein R3 is other than OH.

Embodiment 66. A compound of Formula I wherein R3 is other than OR20.

Embodiment 67. A compound of Formula I wherein when j is 1, and Rl is isopropeyl substituted with at least one RS being halogen, then R24 and R25 are each HL.

Embodiment 68. A compound of Formula I wherein when jis 1, R! is optionally substituted isopropyl, the R24 and R?S are each H.

Embodiment 69. A compound of Formula I wherein when j is 1, then R?4 and R% are each H.

Embodiment 70. A compound of Formula I wherein when j is 1, then R6 is other t han halogen.

Embodiment 71. A compound of Formula I whe rein when j is 1, then R! is other than optionally substituted isopropyl.

Embodiment 72. A compound of Formula I wherein when j is 1, then R1 is cyclopropyl optionally substituted with 1-5 RS, isopropyl, or phenyl optionally substituted with 1-3 R7.

Embodiment 73. A compound of Formula I whe-rein when j is 1, then R1 is cyclopropyl, isopropyl, or phenyl optionally substituted with 1-3 R7.

Embodiment 74. A compound of Formula I wherein when R! is phenyl optionally substituted with 1-3 R7 then R is other th=an cyano.

Embodiment 75. A compound of Formula I wherein R is other than cyano.

Embodiment 76. A compound of Embodiment 5 wherein when R! is phenyl optionally substituted with 1-3 R7 then R is CO,R1%=.

Embodiment 77. A compound of Embodiment 5 wherein R is CO,R1Z. :

Embodiment 78. A compound of Embodiment 8 wherein when R! is phenyl optionally substituted with 1-3 R7 then R2 is CO,RL-2.

Embodiment 79. A compound of Embodiment 8 wherein R2 is CO,R12. : "Embodiment 80. A compound of Formula I wherein when R! is phenyl optionally a. substituted with 1-3 R7 then R24 is H, C(==0)R33, nitro, OR34, S(O);R35 or -

N(R36)RY, and R¥3 is Hor C(=0)R33. :

Embodiment 81. A compound of Formula I wherein when R1 is phenyl optionally substituted with 1-3 R7 then R24 and R25 are each H.

Embodiment 82. A compound of Formula I whe-rein R?4 is H, C(=O)R33, nitro, OR34,

S(0),R35 or N(R36)R37, and R25 is H or €C(=0O)R33. . Embodiment 83. A compound of Formula wherein R24 and R25 are each H.

Embodiment 84. A compound of Formula I wherein when R1 is cyclopropyl or isopropyl optionally substituted with 1-5 . RS, then R is other than

C(=W1N(RP1)S(0),-Re¢ wherein W conmprises at least one atom; RP! comprises at least one atom and Red comprises at least one atom.

Embodiment 85. A compound of Formula I whe:rein when R1 is cyclopropyl optionally substituted with 1-5 R3 or isopropyl optionally substituted with 1-5 RS, then R is other than C(=W1)N(Rb1)S(0),-R¢d wherein W comprises at least one atom;

Rb! comprises at least one atom and R¢d comprises at least one atom.

Embodiment 86. A compound of Formula I whe-rein R is other than

C(=W1)N(RD1)S(0),-Red wherein W comprises at least one atom; Rb1 comprises at least one atom and Red comprises at least one atom.

Embodiment 87. A compound of Embodiment 5 wherein R!8 is H, C;~C, alkyl, hydroxy or C;-C4 alkoxy.

E-mbodiment 88. A compound of Embodiment 8 wherein RE8is H, C(-C4 alkyl, hydroxy or C;—C, alkoxy.

E.mbodiment 89. A compound of Formula I wherein each R= and RY is independently halogen, C;-C; alkyl or C;~C, haloalkyl.

E-mbodiment 90. A compound of Formula I wherein R15 is BF, halogen, C;—C, alkyl,

C1-C4 haloalkyl, hydroxy, C;~C,4 alkoxy or C,—C4 aTkylcarbonyloxy.

Embodiment 91. A compound of Formula I wherein R16 is ¥H, halogen, C{—C alkyl or

C1-C haloalkyl.

Embodiment 92. A compound of Formula I wherein R24 is ¥J, C,-C4 alkyl optionally substituted with 1-2 R30, C,~C, alkenyl! optionally s1abstituted with 1-2 R31, or

C,—C, alkynyl optionally substituted with 1-2 R32; or R24 is C(=O)R33, nitro,

OR34, S(0),R35 or N(RIO)R37,

Emnbodiment 93. A compound of Formula I wherein each R33 is independently H,

C1—C4 alkyl, C;-C3 haloalkyl, C;—~C4 alkoxy, phenoxy or benzyloxy.

Emmbodiment 94. A compound of Formula I wherein R34 js EF, C;-Cy4 alkyl or C;~C3 haloalkyl.

Emmbodiment 95. A compound of Formula I wherein R36 is FJ or C;—C, alkyl. : Exrmbodiment 96. A compound of Embodiment 5 wherein R12 is H; or a radical selected from C;—C, 4 alkyl, C3-C}; cycloalkyl, C4—C;, alkylcycloalkyl, C4~Cj, - cycloalkylalkyl, C,—C,4 alkenyl and C5~Cy4 alkynyl, each radical optionally substituted with 1-3 R27; or -N=C(R35)R56,

Ermbodiment 97. A compound of Embodiment 5 wherein each R27 is independently halogen, hydroxycarbonyl, CC, alkoxycarbonyl, hy-droxy, C;—C, alkoxy,

C;~C4 haloalkoxy, C;—Cy4 alkylthio, C{—C4 haloalkylthio, amino, C;-C, alkylamino, C,—C4 dialkylamino, -CH{O(CH,),} or phenyl optionally substituted with 1-3 R44; or two R27 are taken togethe=r as -OC(0)O- or -O(C(R38)(R38));_,0-; or two R27 are taken together sas an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl moiety.

Ernbodiment 98. A compound of Embodiment 5 wherein R33 is H, C;~Cj alkyl, C;~Cs haloalkyl or C,—C4 alkoxyalkyl.

Combinations of Embodiments 1-98 are illustrated by:

Emnbodiment A. A compound of Formula I wherein

R=2is CO,R12, CH,0R13, CH(OR46)(OR47), CHO, C(=NOR 4)H, C(=NNR48R49)H, (O)CRISHRIE)CO,RIT, C(=0)NR8)R19, C(=S)OR 0, C(=0)SR5,

C(=S)SR52 or C(=NR33)YR4;

R12 is H, -CHEC(O)O(CHy)}, -N=C(R35)R56; or a radical selected from C,—C 4 alkyl, C3-C), cycloalkyl, C4~C, alkylcycloalkyl, C4—Cj, cycloalkylalkyl,

Cy-Cj4 alkenyl, Co~Cj4 alkynyl and phenyl, each radical optionally substituted with 1-3 R27; or

RI2 is a divalent radical linking the carboxylic ester function CO,R12 of each of two pyrimidine ring systems of Formula I, the divalent radical selected from -CH,-, ~(CHj)y-, -(CHp)3- and -CH(CH3)CHj-;

R13 is H, C;-Cj alkyl optionally substituted with 1-3 R28, or benzyl;

R14 js H, C;—Cy alkyl, C;-Cj haloalkyl or benzyl;

R17 is C;—C;q alkyl optionally substituted with 1-3 R29, or benzyl,

R18 is H, C;—C; alkyl, hydroxy, C;—C4 alkoxy or S(0),JR57;

R19is H or C;~C, alkyl; each R27 is independently halogen, cyano, hydroxycarbomyl, C>-C4 alkoxycarbonyl, hydroxy, C;—C4 alkoxy, C;—C4 haloalkoxy, C1—C,4 alkylthio, C1—C, haloalkylthio, amino, C;—C,4 alkylamino, C,—C, dizlkylamino, -CH{O(CHj),} or phenyl optionally substituted with 1-3 R44; or two R27 are taken togethér as -OC(Q)O- or -O(C(R38)(RS8)); ,0-; or two R27 are taken together as an oxygen atom to form, with the carbon atom to which - : they are attached, a carbonyl moiety; RUE

CL each R28 is independently halogen; C;—Cy4 alkoxy, C;—Cg haloalkoxy, C;~C4 a alkylthio, C{—Cj4 haloalkylthio; amino, C{-Cj alkyl amino or Co—C4 : dialkylamino; or two R28 are taken together as an oxygen atom to form, wi th the carbon atom to which they are attached, a carbonyl moiety; each R29 is independently halogen, C;—Cy4 alkoxy, C,—Cg haloalkoxy, C;-Cy4 alkylthio, C;—C,4 haloalkylthio, amino, C;-C4 alkyl amino or C;-Cy dialkylamino; each R#4 is independently halogen, C1—Cy alkyl, C;—~C3 maloalkyl, hydroxy, C1—Cy4 alkoxy, C;-Cj3 haloalkoxy, C1—Cj alkylthio, C;—C3 haloalkylthio, amino, C;-C3 alkylamino, Co—C4 dialkylamino or nitro;

R46 and R47 are independently C|—Cy alkyl or C;—C3 haleoalkyl; or

R46 and R47 are taken together as -CHyCHj-, -CH,CH(CH3)- or -(CHy)3-;

R48 is H, C|-C, alkyl, C,~C4 haloalkyl, C,—C4 alkylcarb=onyl, C,-C4 alkoxycarbonyl or benzyl;

R49 is H, C;-C, alkyl or C,-Cj haloalkyl;

R50, R51 and R52 are H; or a radical selected from C1~Cj.4 alkyl, C3—Cj; cycloalkyl,

C4-C15 alkylcycloalkyl, C4~Cy; cycloalkylalkyl, C5-Cj4 alkenyl and C,—Cy4 alkynyl, each radical optionally substituted with 1-3 R27;

Y is O, S or NRS1,

R33 is H, C;~C; alky1, Cy~Cj haloalkyl, C,~C, alkoxyalkyl, OH or C;~C3 alkoxy;

R54 is C{—Cj3 alkyl, C;~Cj haloalkyl or C,~C, alkoxyalkyl; or

R33 and R54 are taken together as (CHy),-, -CH,CH(CH3)- or (CHy)3-;

R355 and R56 are independently C{—C, alkyl;

R57 is C;—C, alkyl, C1~Cj haloalkyl or NRSIR 60; each R58 is independently selected from H and C;-Cy alkyl;

R59 and R60 are independently H or C;—Cj alkyl;

RS! is H, C,-C; alkyl, C;~Cj haloalkyl or C,~C4 alkoxyalkyl; m is an integer from 2 to 3; and nis an integer from 1 to 4.

Embodiment B. A compound of Embodiment A wherein R3 is halogen.

Embodiment C. A compound of Embodiment B wherein R1 is cyclopropyl or phenyl substituted with a halogen, methyl or methoxy radical in the para position and optionally with 1-2 radicals selected from halogen and methyl in other positions; and R4 is -N(RZ4)R25. ‘ Embodiment D. A compound of Embodiment C wherein R2 is CO,R 12, CH,0R13, :

CHO or CH,CO,R17. -". Embodiment E. A compound of Embodiment D wherein R24 is H, C(O)R33 or C;~C, : alkyl optionally substituted with R30; R25 is H or C;-C, alkyl; or R24 and R23 are taken togeth er as =C(R3I9)NRA)R4L.

Embodiment F. A compound of Embodiment E wherein R2 is CO,R12; and R24 and

R25 are H.

Embodiment G. A compound of Embodiment F wherein R12 is H, C,-C alkyl or benzyl.

Specific embodiments include compounds of Formula I selected from the group consisting of: : methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, 6-amino-5-bromo-22-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt, methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, phenylmethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt, ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, methyl 6-amino-5-<hloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate, ethyl 6-amino-5-ch. loro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate, 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid,

ethyl 6—amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate, methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate,. and 6-amineo-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid.

Also notewvorthy as embodiments are herbicidal compositions of the pres-ent invention comprising the compounds of embodiments described above.

This invermtion also relates to a method for controlling undesired vegetatio-n comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e-g., as a composition described herein). Of note as embodimerts relating to methods of use zare those involving the compounds of embodiments described atoove.

Of note is a compound of Formula I, including all geometric and stereoisomers,

N-oxides or agriculturally suitable salts thereof, agricultural compositions corataining them and their use as herbicides wherein R2 is CO,R!2, CH,OR13, CHO, CC(=NORI4H,

CRIS)RI6)CO5R17 or C(=0)N(R18)R19; each R7 is independently halogen, C;—Cj4 alkyl,

C1—C; haloalkyl, C;-C3 alkoxy, C;-C3 haloalkoxy, C;-C3 alkylthio or C;-C3 haloalkylthio; R_12 is H; or a radical selected from CC 4 alkyl, C3—Cy5 cycloalkyl, C4—Cia alkylcycloalkyl, C4—C,, cycloalkylalkyl, C,—Cj4 alkenyl and C,—C;4 alkynyl, each radical “optionally subst ituted with 1-3 R27; R13 is H, C;-C) alkyl optionally substitLated with 1-3

R28 or benzyl; R14 is H, C;~C, alkyl or C;—C4 haloalkyl; RS and R16 are independently H, "halogen, Ci-Cx alkyl, C; C4 haloalkyl, hydroxy or C;-C alkoxy; R17 is &|—Cjq alkyl optionally substituted with 1-3 R22 or benzyl; R18 and R19 are independently= H or C;-Cy alkyl; each R27 is independently halogen, hydroxycarbonyl, C,—C, alkzoxycarbonyl, hydroxy, C;—C~ alkoxy, C;—Cy haloalkoxy, C;—Cy alkylthio, C1—C4 haloalky~lthio, amino,

C1—C4 alkylam-ino, C,—Cy4 dialkylamino, -CHFO(CHy),} or phenyl optionalRy substituted with 1-3 R¥4; ox two R27 are taken together with the carbon atom to which thewy are attached to form a carbeonyl moiety; each R28 and R29 is independently halogen, C 1-Cy4 alkoxy,

C;-C4 haloalkoxy, C;~Cy4 alkylthio, C;—C4 haloalkylthio, amino, C;-Cy a lkylamino or

C,—C, dialkylamino; each R30, R3! and R32 is independently halogen, hydroxy, C;~Cy4 alkoxy, C;—C.g haloalkoxy, C;-C4 alkylthio, C;~C4 haloalkylthio, ammino, C;-C, alkylamino, C, —Cy4 dialkylamino or C,—C, alkoxycarbonyl; each R38 is i ndependently halogen, C;-C3 alkyl, C;-C; alkoxy, C;-C3 haloalkoxy, C;-C3 alkylthio, C;-C; haloalkylthio, saamino, C;—C; alkylamino, C,—C, dialkylamino or C»—-C, alkzoxycarbonyl; each R44 is inde=pendently halogen, C,—C4 alkyl, C;—Cj haloalkyl, hydroxy, CC;-C,4 alkoxy,

C;-C; haloalkosxy, C,~C4 alkylthio, C;—Cj haloalkylthio, amino, C,-Cj3 alkylamino, C,-Cy4 dialkylamino or nitro; m is an integer from 2 to 5; and n is an integer from 1 wo 4. Also of note is a compound of Formula I, including all geometric and stereoisomers , N-oxides or agriculturally suitable salts thereof, agricultural compositions containing them and their use as herbicides wsherein each R3 and RS is independently halogen, C1—-C; allkyl or Cy-C, haloalkyl; R13 i s H, halogen, C;—-C,4 alkyl, C;—C4 haloalkyl, hydroxy, C;-C,4 alkoxy or Cp—

C, alkylcarbonyloxy; R16 is H, halogen, C;~C, alky) or C;~C, haloalkyl; R? is H, C;-Cy4 alkyl optionally substituted with 1-2 R30, C,—C alkenyl optionally substituted with 1-2

R31, or C,—C, alkynyl optionally substituted wisth 1-2 R32; or R# is C(=O)R33, nitro,

OR34, S(O),R33 or N(R36)R37; each R33 is indepe=ndently H, C{-C, alkyl, C;-C3 haloalkyl,

C;=C, alkoxy, phenoxy or benzyloxy; R34 is H, C-1-C, alkyl, C;—C; haloalkyl; and R36is H or C;—C, alkyl.

The compounds of FormulaI can be pregpared by one or more of the following methods and variations as described in Schemes 1 through 7 and accompanying text. The definitions of R, R], RZ, R3, R4, RS, RS, R7, RI2- R13, R14, R15, R16, R17, R18, R19, R20,

R21 R22 R23 R24, R25, RZ7, R28, R29, R30, R31. R32 R33, R34, R35, R36, R37, R38, R39,

R40, R41, R42 R43 RH, R45, R46, R47, R48, R49®, R50, RS], R52, R33, R54, R55, R56, RYT,

R58, R59, R60, R61, Y, j, k and n in the compounds of Formulae I through 12 below are as defined above in the Summary of the Invention and description of embodiments unless otherwise indicated. a

Compounds of Formula I can be prepared from chlorides of Formula 2 by reaction with amines of Formula 3, optionally in the pre=sence of a base such as triethylamine or" potassium carbonate as outlined in Scheme 1. The reaction can be run in a variety of” . solvents including tetrahydrofuran, p-dioxane, ethanol and methanol with optimum.

Lo temperatures ranging from room temperature to 200°C. The method of Scheme 1 is. © illustrated in Step C of Example 1, Steps D1 and D2 of Example 2, and Step B of Example= 4. . .

Scheme 1 : 2 + HNR2HRS ——

RN a 3 2

Compounds of Formula 2 can be preparecd from hydroxy compounds of Formula 48 (which may exist in the keto form) by reaction with a chlorination reagent such as phosphorous oxychloride or thionyl chloride, op-tionally in the presence of a base such as

N,N-dimethylaniline as shown in Scheme 2. The reaction can be run neat or in the presence of a solvent such as N,N-dimethylformamide at temperatures ranging from room temperature to 120 °C. The method of Scheme 2 is illustratecd in Step C of Example 1, Steps C1 and C2 of Example 2, and Step B of Example 4.

Scheme 2 rR = POCly pg — 2 2

RY a OH or SOC, 4

Compounds of Formula 4 can be prepared by the condensation of amidines of Formula 5 with keto esters of Formula 6 in solvents such as methanol or ethanol at temperatures ranging from room temperature to the reflux temperature of the solvent as shown in Scheme 3. Optionally a base such as a metal alkoxide or 1,1,3,3-tetramethylguanidine may be employed. The method of Scheme 3 is illustrated in Step A of Examples 1 and 4, and Steps

Al and A2 of Example 2.

Scheme 3 . wd or ——ee 4 .

Ca wy 7 K RL 5 6 wherein R80 is a carbon moiety such as alkyl, preferably C;—C; alkyl.

Compounds of Formula 4 wherein R3 is a halogen can be prepared from compounds of

Formula 4 wherein R3 is hydrogen by reaction with a halogen such as bromine or a halogenating reagent such as an N-halosuccinimide or a sulfuryl halide in a variety of solvents including acetic acid, N,N-dimethylformamide, dichloromethane and carbon tetrachloride at temperatures ranging from 0-100 °C as shown in Scheme 4. The method of

Scheme 4 is illustrated in Step B of Example 1, and Steps B1 and B2 of Example 2.

Scheme 4 halogenating reagent 4 —_— 4 ®R3is H) (R3 is halogen)

Also, compounds of Formula I wherein R3 is a halogen can be prepared from compounds of Formula I wherein R3 is hydrogen by reaction with a halogenating reagent analogous to the method of Scheme 4. This alternative method is illustrated in Step C of

Example 4.

A particularly use ful preparation of compounds of Formula 4 wherein R3 is a halogen and R2 is CO,R!2 is the reaction of compounds of Formula 4 where R3 is hydrogen and R? is CH(OR!2), with a halogenating reagent and oxidizing reagent such as an

N-halosuccinimide or bromine (when R3 is bromine) in a solvent such as dichlorormethane, 5S trichloromethane or tetrachloromethane at temperatures ‘ranging from room temperature to the reflux temperature off the solvent as shown in Scheme 5.

Scheme 5

Br, (for R3is Br) 4 —_— 4 (R2is CHOR12)y * 9 (R2is CORIZ;

R3is H) R3is H)

N-R3 ®R3is halogen) 0

Compounds of Foranula 5 and 6 are either commercially available or can be prespared by known methods. (For example see: P. J. Dunn in Comprehensive Organic Functional

Group Transformations, A.R. Katritzky, O. Meth-Cohn, C.W. Rees Eds, Pergamon Press; ~

Oxford, 1995; vol. 5, pp.741-782; T.L. Gillchrist in Comprehensive Organic Functional :

Group Transformations, _A. R. Katritzky, O. Meth-Cohn, CW. Rees Eds., Pergamon Press;

Oxford, 1995; vol. 6, pp. 601-637 and B. R. Davis, P. J. Garratt in Comprehensive Organic

Synthesis, B. M. Trost Ed, Pergamom Press; Oxford, 1991; vol. 2, pp. 795-803.)

Alternatively compounds of Formula I can be prepared from correspo nding compounds of Formula 7 wherein X1 is a leaving group, such as a halogen or alkylsullfonyl group (e.g., methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl), as shoven in

Scheme 6.

Scheme 6 2 .

R3 MIRL 8 = Lic coms . > I lis optionally substituted

PN Pd catalyst cyclopropyl, isopropyl or phenyl)

X R4 7 wherein M! is B(OH),, Sn (n-Bu)3, MgX! or ZnX1; R! is optionally substituted cyclopropyl, optionally substituted isopropyl or optionally substituted phenyl; and X! is a leaving gro=p.

This method involves palladium-catalyzed reaction of a compound of Formula 7 with a compound of Formula 8 ira the form of a boronic acid (e.g., M! is B(OH),), an orgaraotin reagent (e.g., M! is Sn(n-Bu)3), a Grignard reagent (e.g., M! is MgX1) or an or-ganozinc reagent (e.g., M! is ZnX 1). (For example see: N. Ali, A. McKillop, M. Mitchell, R.. Rebelo,

A. Ricardo, P. Wallbank:, Tetrahedron, 1992, 48, 8117-8126; J. Solberg, K. Undhesim, Acta

Chem. Scand., 1989, 43, 62-68, V. Bonnet, F. Mongin, F. Trécourt, G. Quéguminer and

P.Knochel, Tetrahedroz, 2002, 58, 4429-4438.)

Compounds of Formula 7 wherein X! is a halogen can be prepared frorm dihalo compounds of Formula 12 with an amine of Formula 3 optionally catalyzed by a base such as triethylamine or potassium carbonate in a variety of solvents including tetrahydrofuran and dichloromethane at temperatures ranging from 0 °C to the reflux temperatume of the solvent as shown in Scheme 7.

Scheme 7 2 3 3 = R . or —— >» 7 (Xlis halogen) xk x x1 : 12 (Xlis halogen)

Compounds of Formula 12 can be prepared by known methods. ‘(For example, see

H. Gershon, J. Org. Chera., 1962, 27, 3507-3510.)

As shown in Scherme 8, compounds of Formula I wherein RZ is CO,R12 camm also be prepared from compounds of Formula 13 by means of a carbonylation reaction. Typical conditions are 1-10 atmoespheres of carbon monoxide in the presence of a palladium. catalyst - in a mixture of an alcohol and another solvent such as N,N-dimethylformamide, N—methyl- pyrrolidinone or tetrahydrofuran at temperatures ranging from room temperature to 1 50 °C.

Scheme 8 x2 3 x © —_— » I ®2 is CO,R12)

A Z - Pd catalyst

RI20H 13 x=2isClorBn

As shown in Scheme 9, compounds of Formula 13 can be prepared from compounds of Formula 14 by reactiom with amines of Formula 3 in a reaction analogous to the method of Scheme 1.

Scheme 9 x F 3

PS _ 13

R 7 x 14

As shown in Scheme 10, compounds of Formula 14 can be prepared from diols of

Formula 15 by reaction with a halogenating agent such as phosphorous oxychloride or phosphorous oxybromide in a reaction analogous to the method of Scheme 2. (See H.

Gershon, R. Braun, A. Scala and R. Rodin, J. Med. Chem 1964, 7, 808-811 and M. H.

Norman, N. Chen, Z. Chen, C. Fotsch, N. Han, R. Huet, T. Jenkins J. Kincaid, L. Liu, Y. Lu,

O. Moreno, V. J. Santora, J.D. Sonnenberg and W. K arbon, J. Med. Chem, 2000, 43, 4288 4312 for examples of this method and for examples ofS preparation of compounds of Formula 15)

Scheme 10

H oo : : Co EN R3 " POCl3 or POBr—3 : ———> 14 X2isClorBr . ZF

R OH

Compounds of Formula X wherein R2 comprises an ester function (e.g., CO,R!2 wherein R12 is other than H) can be prepared from corresponding carboxylic acid 15 compounds of Formula I (e.g., wherein R12 js H) by a wide variety of esterification methods known in the art. One method is illustrated in Example 3. Conversely, carboxylic acid compounds of Formula I can be prepared from the corresponding ester compounds by a wide variety of hydrolysis methods known in the art, such as saponfication.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formulal may not be ceompatible with certain functionalities present in the intermediates. In these instances, the imcorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, T. W. Greene, P. G. M. Wuts, Protective Groups in

Organic Synthesis, 2nd ed.; Wiley: New York, 1991». One skilled in the art will recognize that, in some cases, after the introduction of a gi ven reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compeounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formmula I.

One skilled in the art will also recognize thwat compounds of Formulal and the intermediates described herein can be subjected ten various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that ore skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, amd not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative= run whose procedure is described in other Examples or Steps. Percentages are by weighat except for chromatographic solvent mixtures or where otherwise indicated. Parts and pemcentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “d” means doublet, “t” means triplet, : “q” means quartet, “m” means multiplet, “dd” meains doublet of doublets, “ddd” means doublet of doublets of doublets, “dt” means doublet of triplets, “dq” means doublet of quartets, “br s” means broad singlet, “br d” means broad doublet.

EXAMPLE 1 :

Preparation of ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 1) and methyl 6-amino-5-bromo-2-cyclopropyl<4-pyrimidinecarboxylate (Compound 2)

Step A: Preparation of 2-cyclopropyl-6-(diethoxz ymethyl)-4(1H)-pyrimidinone

To a mixture of ethyl 4,4-diethoxy-3-oxobutanozate (prepared according to the method of E. Graf, R. Troschutz, Synthesis, 1999, 7, 1216; 10.0 g, 46 mmol) and cyclopropane- carboximidamide monohydrochloride (Lancaster Syn=thesis, 5.0 g, 41 mmol) in methanol (100 mL) was added a methanol solution of sodium rmethoxide (5.4 M, 8.4 mL, 46 mmol).

The reaction mixture was stirred overnight. The solvent was removed with a rotary evaporator. Dichloromethane was added and the mixtwire was filtered. The solvent from the filtrate was removed with a rotary evaporator. The residue was purified by medium pressure liquid chromatography (MPLC) (35—100% ethyl acetate in hexanes as eluant) to afford the title compound as a white solid (4.67 g). 1H NMR (CDCl) § 6.55 (s, 1H), 5.10 (s, 1H), 3.61 «(m, 4H), 1.91 (m, 1H), 1.23 (m, 8H), 1.09 (m, 2H).

Claims (1)

1. CLAIMS What is claimed is:

   1. A compound selected from Fommula I, an N-oxide or an agriculturally suitable salt thereof, 2 - . Rl XN - : wherein R! is cyclopropyl optionally substittated with 1-5 R5, isopropyl optionally substituted "with 1-5 RS, or phenyl option ally substituted with 1-3 R7; R2is (0); CRISRI6)LR; R is CO,H or a herbicidally effective derivative of CO H; R3 is halogen, cyano, nitro, OR20, SR2! or N(R22)R23; R4 is -NR24)R%5 or -NO»; each RS and R'is independently haJogen, C=C alkyl, C;—Cg haloalkyl, C,-Cg alkenyl, C,—Cg¢ haloalkenyl, C;-Cj alkoxy, C;~C; haloalkoxy, C1—Cj alkylthio or C;—C, haloalkylthio; each R7 is independently halogen, cyano, nitro, C;—C, alkyl, C1-C, haloalkyl, C3-Cg : cycloalkyl, C3—Cg halocycloalkyl, C1—Cy4 hydroxyalkyl, C»-C, alkoxyalkyl, C,-C4 haloalkoxyalkyl, Co—CC, alkenyl, C,~Cy haloalkenyl, C3~C4 alkynyl, C3—C4 haloalkynyl, hydroxy. C;-C4 alkoxy, C;—C,4 haloalkoxry, Co-Cy alkenyloxy, C,~C4 haloalkerayloxy, C3—-Cy4 alkynyloxy, C3-C4 haloalkynyloxy, C,—C4 alkylthio, C;—Cy4 haloalkylthio, C,—C, alkylsulfinyl, C;-Cy4 haloalkylsulfinyl, C—C4 alk-ylsulfonyl, C,-C4 haloalkylsulfonyl, C)—C4 alkenylthio, CoC haloalkemylthio, Co—C, alkenylsulfinyl, Co~C4 haloalkenylsulfinyl, C,—C,4 alkenylsulfonyl, C—Cy4 haloalkenylsulfonyl, C3-C4 alkynylthio, C3-C4 haloalkynylthio, C3~C4 alkynylsuifinyl, C3-Cq4 haloalkynylsulfinyl, C3~C,4 aalkynylsulfonyl, C3~Cy4 haloalkynylsulfonyl, C1~Cy alkylamino, C,—Cj dialkylarnino, C3—Cg cycloalkylamino, C4—Cg (alkyl)cycloalkylamino, C,—Cg alkylcarbonyl, C,~Cg alkoxycarbonyl, Co—Cg alkylaminocarbonyl, C;~Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl, phenyl, phenoxy and 5- or 6-membe=red heteroaromatic rings, each phenyl, phenoxy and 5- or 6-membered heteroaro-matic ring optionally substituted with one to three substituents independently selected from R43; or two adjacent R7 are taken together as -OCH,€0-, -CH,CH,O-, -OCH(CH3)O-, -OC(CHz),0-, -OCF,0-, -CF,CF,0-, —OCF,CF,0- or -CH=CH-CH=CH-;

   R15 is H, halogen, C;~C, alkyl, C;—C, haloalkyl, hydroxy, C;~C, alkoxy or C,~Cy alkylcarbonyloxy;

   R16 js H, halogen, C;—C, alkyl or C;—C4 halealkyl; or

   R15 and R16 are taken together as an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl mo-ety;

   R20 is H, C;-C; alkyl or C;~Cj haloalkyl;

   R2! js H, C;—C, alkyl or C;~C3 haloalkyl;

   R22 and R23 are independently H or C;~C, alkyl;

   R24 js H, C;-C, alkyl optionally substituted with 1-2 R30, C,~C, alkenyl optionally substituted with 1-2 R31, or C,—C, alkyny} optionally substituted with 1-2 R32; or R24 is C(=0)R33, nitro, OR34, S(0),R3S, N(R36)R37 or N=C(R62)R63;

   R25 js H, C;-Cy alkyl optionally substituted ~with 1-2 R30 or C(=0)R33; or

   R24 and R25 are taken together as a radical selected from -(CHy)y-, -(CHy)s-, -CH,CH=CHCHj,- and -(CH,),0(CH3 ),-, each radical optionally substituted with 1-2 R38; or

   R24 and R25 are taken together as =C(RION (R40)R#! or =C(R42)OR43;

   each R30, R31 and R32 is independently haloggen, C;—Cj alkoxy, C1~C3 haloalkoxy,

   C~C; alkylthio, C;~C haloalkylthio, amino, C;~Cj alkylamino, C,—Cy dialkylamino or C,—C, alkoxycarbonyl; . each R33 is independently H, C;—C 4 alkyl, C;—Cj haloalkyl, C;—C, alkoxy, phenyl, : phenoxy or benzyloxy; : B R34 is H, C;-Cj4 alkyl, C;—C; haloalkyl or C HR6C(O)ORSE7; R35 is C;—C, alkyl or C;—C; haloalkyl;

   R36 is H, C;~C, alkyl or C(=0)R54;

   R37 is H or C—C4 alkyl;

   each R38 is independently halogen, C;—C3 aLkyl, C;—Cj alkoxy, C;—C3 haloalkoxy, C;-C; alkylthio, C;-Cj haloalkylthio, amino, C;—-C3 alkylamino, C>—Cy4 dialkylamino or C,—C, alkoxycarbony 1; R39 is H or C;~C,4 alkyl; R40 and R4! are independently H or C{—C,4 alkyl; or R40 and R4! are taken together as -(CHp)4-, —(CHa)s-, -CH,CH=CHCH,- or -(CHp),O(CHy)-; R42 is H or CC, alkyl; R43 is C1—C4 alkyl; each R45 is independently halogen, cyano, nitro, C;—Cj alkyl, C;-C4 haloalkyl, C3-Cg cycloalkyl, C3—Cg halocycloalkyl, C;—Cy alkenyl, Co—Cy4 haloalkenyl, C3-C4 a alkynyl, Cs~C; haloalkyl, GC alkoxy, C—Cy haloalkoxy, C;-Cy alkylthio, C=C; Hatoalkylihio, CC alkylsiifiny], C-Cj alkylsufonyl, C;-Cf akylatnino, C5-Cy diblicyldmino, €5-Cg Gycloaliylamino; C-Cg™ + (alkyl)cycloalkylamino, CC alkyloarbomyl, Cog-C alkoxycarbonyl, Cy-Cg R62 is FH, CLC all of phenyl Sptionally substituted “with [-FRES; = =< +7 RSEHerCiCyalghor ABET wiaps oo R62 and R63 are taken together as (CHp)y- of (CHaJ5=; **" % Lr R64 js H, Cy~Cyy alkyl, C4~C; haloalkyl, Cy—Cy alkox”y, phenyl, pherioxy or benzyloxy; SE Co CL each RES is independently CH, C1 or OCH; ~ R66 is H, C;-C; alkyl or C}~Cy alkoxy; } :

   a. R67 isH, C;-C;4 alkyl or benzyl; ; "jisOor1; and - : oo - kis Oor I; pro=vided that: : : (a) when kis 0, then jis 0; . : (b) when R2 is CH,OR? wherein R? is H, optionally’ substituted alkyl or benzyl, then : R3is other than cyano; ~~ © . . 20 (c) when R1 is phenyl substituted by Cl in each of the meta positions, the phenyl is . also substituted by R7 in the para position; (@) when R! is phenyl substituted by R7 in the para position, said R7 is other than tert-butyl, cyano or optionally substituted phenyl; . (e) when R! is cyclopropyl or isopropyl optionally subsEituted with 1-5 RS, then R is other than C(=W)N(RP)S(0),-R¢-Rd wherein W is C3, S, NRe or NOR®; Rb is hydrogen, C1—Cj4 alkyl, C,—Cg alkenyl or Cp—Cg alkynyl; R¢ is a direct bond or } CHR, O, NR® or NOR®; RY is an optionally substitufed heterocyclic or carbocyclic aromatic radical having 5 to 6 ring atoms, the radical being optionally condensed with an aromatic or nonaromatic 5- or 6-membered rEng; each R¢ is independently H, C;~C; alkyl, C;—Cj haloalkyl or phenyl; and Rf iss H, C;~C; alkyl or phenyl;

   i. ~ and -

   ~. (f) the compound of Formula I is other than diethyl 6-am_ino-5-nitro-2-phenyl-4-pyrimidinemalonate ; or 4-amino-5-cyano-6-2-hydroxyethoxy)-2-phenylpyr-imidine. :

   } 2. The compound of Claim 1 wherein . R2 is CO,R12, CH,0R13, CH(OR46)(OR#7), CHO, C(=]NFORI4H, C(=NNR*R49)H, (O);CRIHRIEYCORY, C(=O)NRI®RI, C(=S)OR3?, C(=0)SR>], C(=S)SR52 or C(=NR33)YR54; sMENDED SHEET 2007 -07- 86°

   R12 is H, -CH{C(0)O(CHy)3}, -N=C(R55)R5®; or a radical selected from C;—Cy4 alkyl, CC cycloalkyl, C4—Cy, alkyleycloalkyl, C4-C;, cycloalkylalkyl, C,—C,4 alkenyl, C,—Cy4 alkynyl and phesnyl, each radical optionally substituted with 1-3 R27; or

   R12 js a divalent radical linking the carboxylic= ester function CO,R 12 of each of two pyrimidine ring systems of Formula I, thme divalent radical selected from -CHj-, -(CHy)y-, (CHp)3- and -CH(CH3)CH,- 3

   R13 is H, C;—Cy alkyl optionally substituted with 1-3 R28, or benzyl;

   R14 is H, C;~C, alkyl, C=C haloalkyl or berazyl;

   R17 is C)-C alkyl optionally substituted with 1-3 R29, or benzyl;

   R18 js H, C,~C; alkyl, hydroxy, C;—Cj alkoxy or S(O);R57;

   R19is H or C,-C, alkyl;

   each R27 is independently halogen, cyano, hycroxycarbonyl, C;—Cy4 alkoxycarbonyl, hydroxy, C;-C4 alkoxy, C3~C, haloalkoxy, C;—C4 alkylthio, C1-C4 haloalkylthio, amino, C1—C alkylamino-, C,~Cy dialkylamino, -CH{O(CHp),} or phenyl optionally substituted with 1-3 R244; or two R27 are taken together as -OC(0)O- or -O (CR3*)(R58));_0-; or two R27 are taken together as an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl moiety;

   each R28 is independently halogen, C,—C, alk=oxy, C;—C4 haloalkoxy, C;-C4 : alkylthio, C;—Cj haloalkylthio, amino, C-Cy alkylamino or Cx~C4 dialkylamino; or ~ two R28 are taken together as an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl moiety;

   each R29 is independently halogen, C,—Cj alkoxy, C;—-Cy haloalkoxy, C;—Cy alkylthio, C;-Cj haloalkylthio, amino, C1~C, alkylamino or Cy-Cy dialkylamino;

   each R44 is independently halogen, C1~C alk=yl, C;—C3 haloalkyl, hydroxy, C1-C4 alkoxy, C;-Cj haloalkoxy, C;—C3 alkylthio, C;—C3 haloalkylthio, amino, CC;

   alkylamnino, C,-C dialkylamino or nitro;

   R46 and R47 are independently C;-C4 alkyl or= C1—C3 haloalkyl; or R46 and R47 are taken together as -CHyCH,-, -CH,;CH(CH3)- or -(CHa)3-; R48 is H, CC, alkyl, C;—C4 haloalkyl, Co—Cy alkylcarbonyl, Co—C4 alkoxycarbonyl or benzyl; R49 is H, C1—C4 alkyl or C;—C4 haloalkyl;

   R50, R51 and R52 are H; or a radical selected frorm Cy~C14 alkyl, C3~C) cycloalkyl, C4-C,; alkylcycloalkyl, C4—C;5 cycloalkylalkyl, Cp—C;4 alkenyl and Cp—Cy4 alkynyl, each radical optionally substituted with 1-3 R?7; Y is O, S or NRS!; R53 is H, C{—Cj3 alkyl, C;~Cj haloalkyl, C,—C,4 alkoxyalkyl, OH or C;—Cj; alkoxy; R34 is C;~C5 alkyl, C;—C5 haloalkyl or C,—C,4 alkoxyalkyl; or R53 and R54 are taken together as -(CH,),-, -CH5CH(CHj)- or -(CHy)3-; R35 and R56 are independently C;~C, alkyl; R57 is CC, alkyl, C,~Cj haloalkyl or NR3°R60; each R38 is independently selected from H and C1-C, alkyl; R39 and ROD are independently H or C;—C,4 alkyl 5 R61 is H, C;-Cj5 alkyl, C;—C, haloalkyl or Co—C_4 alkoxyalkyl; m is an integer from 2 to 3; and n is an integer from 1 to 4.

   3. The compound of Claim 2 wherein R3 is halogen. ~~ -

   4. The compound of Claim 2 wherein R! is cyclopropyl or phenyl substituted with . a halogen, methyl or methoxy radical in the para positi on and optionally with 1-2 radicals selected from halogen and methyl in other positions; arid R% is -NRZ#)R2, _

   : 5. The compound of Claim 4 wherein R2 is COR 12, CH,OR13, CHO or CH,CO,R17.

   6. The compound of Claim 5 wherein R24 is BJ, C(O)R33 or C;-C, alkyl optionally substituted with R30; R25 is H or C;—C; alkyl; or R24 ;and R25 are taken together as =C(R3 NHNR4AO)R4! .

   7. The compound of Claim 6 wherein R2 is CCO,R!2; and R24 and R?> are H.

   8. The compound of Claim 7 wherein R12 is JH, C,—C4 alkyl or benzyl.

   9. The compound of Claim 1 selected from the group consisting of: methyl 6-amino-5-bromo-2-cyclopropyl-4-py-rimidinecarboxylate, ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimnidinecarboxylate, phenylmethyl 6-amino-5-bromo-2-cycloprop=yl-4-pyrimidinecarboxylate, 6-amino-5-bromo-2-cyclopropyl-4-pyrimidin ecarboxylic acid monosodium salt, methyl 6-amino-5-chloro-2-cyclopropyl-4-py-rimidinecarboxylate, phenylmethyl 6-amino-5-chloro-2-cycloprop=yl-4-pyrimidinecarboxylate, 6-amino-5-chloro-2-cyclopropyl-4-pyrimidin«ecarboxylic acid monosodium salt, ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyriamidinecarboxylate, methyl 6-amino-5-chloro-2-(4-chlorophenyl)—4-pyrimidinecarboxylate, ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4—pyrimidinecarboxylate,

   6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarb>oxylic acid, ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidimecarboxylate, methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimi«dinecarboxylate, and 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecar®boxylic acid.

   10. A herbicidal mixture comprising a herbicidally effective amount of a compound of Claim 1 and an effective amount of at least one additional ac#ive ingredient selected from the group consisting of an other herbicide and a herbicide safener.

   11. A herbicidal mixture comprising synergistically effexctive amounts of a compound of Claim 1 and an auxin transport inhibitor.

   12. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

   13. A method for controlling the growth of undesired vesgetation comprising contacting the vegetation of its environment with a herbicidally effective amount of a compound of Claim 1. :

   14. A herbicidal composition comprising a herbicidally effective amount ofa compound of Claim 1, an effective amount of at least one additIonal active ingredient’ . ’ selected from the group consisting of an other herbicide and a hmerbicide safener, and at least -. “one of a surfactant, a solid diluent or a liquid diluent.