AU656868B2 - Intermediate useful in the production of pyrimidine derivatives having herbicidal activity - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): SUMITOMO CHEMICAL COMPANY, LIMITED A.R.B.N. 007 509 999 Invention Title: INTERMEDIATE USEFUL IN THE PRODUCTION OF PYRIMIDINE DERIVATIVES HAVING HERBICIDAL ACTIVITY *0 0 0 The following statement is a full descriptiolni&. this invention, including the best method of performing it known to me/us: -IA INTERMEDIATE USEFUL IN THE PRODUCTION OF PYRIMIDTNE DERIVATIVES HAVING HERBICIDAL ACTIVITY.

This application is divided from our copending application no. 33971/93 which was divided from no. 76467/91 (635839) ard relates to a novel compound disclosed therein as an intermediate in the production of pyrimidine derivatives having herbicidal activity.

Briefly stated, the present invention provides a compound of the formula and a method for its production, as will be described in detail below: 0 Y3 U z\ COA Y2 XEH (2) y1 BACKGROUND OF THE INVENTION In the abovementioned copending application 76467/91 we have described and claimed a pyrimidine derivative having the formula

*O

y3 Z COA y2 1

N

N

R

2 wherein A is C 3

-C

8 cycloalkyl C-C 6 alkyl, C 3 cycloalkyl

CI-C

6 alkyl substituted with at least one member selected from the group consisting of Ci-C alkyl, C 1

-C

6 alkoxy, halo

CI-C

6 alkyl, Ci-C 6 alkoxy- 1 carbonyl and halogen, C 3

-C

6 oxacycloalicyl, C 3

-C

6 oxacycloalkyl substituted with at least one member selected froma the group consisting of Cl-C 6 alkyl, Cr-C 6 alkoxy, halo C 1

-C

6 alkyl, C 1

-C

6 alkoxycarbonyl and halogen, C 3 -c 6 oxadycloalkyl C 1

-C

6 alkyl, C 3

-C

6 oxacycloalkyl Cr-C6 alkyl substituted with at least one member selected from the group consisting Of Cy-C 6 alkyl, CI-C 6 alkoxy,.halo Cr-CE alkyl, Cl-C 6 alkoxycarbonyl and .halogen, C 3

-C

5 dioxacycloalkyl, C.

3 -CS dioxacycloalkyl substituted with at least one member selected from the group consisting Of CI-C 6 alkyl, Cl-C 6 alkoxy, halo C 1

-C

6 alkyl, Cl-Cs alkoxycarbonyl and halogen, C 2

-C

5 dioxacycloalkyl Cl-C 6 alkyl or C 2

-C

5 dioxacycloalkyl C 1

-C

6 alkyl substituted. ;with at least one mber selected from the group consisting Of C 1

-C

6 alkyl, CI-C 6 alkoxy, halo Cr--C6 alkyl, C 1

-C

6 alkoxycarbonyl and halogen; each of RI and R 2 which may be the same or differnt, is C 1

-C

6 alkyl, CI-C 6 alkoxy, halo Cl-C 6 alkoxy or halogen;

S

*5 0 S S *~tS S S.

S

S. 0 S. S 0* *5 25

S

0.05 X is oxygen or sulfur; Z is nitrogen or Cy 4 each of yl, y2 and y3, which may be the same or different, is hydrogen, halogen, Cl-C6 alkyl or Cr-Cs alkoxy; and Y4 is hydrogen, hydroxyl, mercapto, nitro, halogen, C 1

-C

6 alkyl, C 2

-C

6 alkenyl, C 2 -C6 alkynyl, C 1

-C

6 alkoxy, C 3

-C

6 alkenyloxy, C 3

-C

6 alkynyloxy, halo Cl-C 6 alkyl, halo C 2

-C

6 alkenyl, halo C 2 -C6 alkynyl, halo C 1

-C

6 3 1alkoxy, halo C 3

-C

6 alkenyloxy, halo C 3 -C6 alkynyloxy, Cj-C6 alkoxy CI 1

-C

6 alkyl, C 3

-C

6 alkenyloxy C 1 -C6 alkyl,

C

3 -C6 alkynyloxy c 1 -C6 alkyl, cyano, formyl, carboxyl, CI-Cs alkoxycarbonyl, C 3

-C

6 alkenyloxycarbonyl, C 3

-C

6 alkynyloxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of

C

1

-C

6 alkyl, Cl-C6 alkoxy, halo C 1

-C

6 alkyl, Cl-C 6 alkoxycarbonyl and halogen, phenoxy, phenoxy substituted with at least one member selected from the group consisting of C 1

-C

6 alkyl, CI-C6 alkoxy, halo CI-C6 alkyl, Cl-C 6 alkoxycarbonyl and halogen, phenylthio, phenylthio substituted with at least one member selected from the group consisting Of Cl-Cs alkyl, Cl-C6 alkoxy, halo C 1 -C6 alkyl, Cl-C6 alkoxycarbonyl and halogen, benzyloxy, benzyloxy substituted with at least one member selected from the group consisting Of Cl-C6 alkyl, Cj-C 6 alkoxy, halo Cl-Cs alkyl, C 1

-C

6 alkoxycarbonyl and halogen, benzylthio, benzylthio substituted .:with at least one member selected from the group consisting of Cl-C6 alkyl, Cl-C 6 alkoxy, halo Cl-Cs alkyl, C 1 -C6 alkoxycarbonyl and halogen,

~R

-R6 wherein each of R5 and R6, which may be the same or different, is hydrogen, C 1 -Cr, alk C3-C6 alkenyl or

C

3 -C6 alkynyl, 4 0

R

6 wherein R5 and R 6 are as defined above, -S -R 7

(O)M

wherein R 7 is C 1

-C

6 alkyl, C 3

-C

6 alkenyl or C 3

-C

6 alkynyl and m is an integer of 0, 1 or 2, 0 wherein X1 is oxygen or sulfur, and R 7 is as defined 5 above, or

S

0*

S

S

S

S. S S S 5- S. S S

S

V S *5 S S. S S 55 S 55 OS S

S

OS

S S

S

S

M

wherein R 7 and m are as def ined above, and n is an integer of from 1 to 4; a method for producing the pyrimidine derivative (1) which comprises reacting a compound having the formula, 0 y3 II z COA y2 (2) Y1 1 wherein A, X, Z, yl, Y2 and Y3 are as defined above, with a compound having the formula,

R

1

N

W (3)

N

\Rz wherein each of R1 and R 2 are as defined above; W is halogen or S-R8 (0) 5 wherein R 8 is C 1

-C

6 alkyl, benzyl or benzyl substituted with at least one member selected from the group consisting of CI-C 6 alkyl, C 1

-C

6 alkoxy, halogen or nitro; and e is an integer of 0, 1 or 2; a method for producing the pyrimidine derivative (1) 1.0 which comprises the steps of o 0 reacting a carboxylic acid derivative having the formula 0 y3 11 S z I COH

RI

N

y2 x (4) Yi N R2 1 wherein X, Z, yl, y2, y3, R1 and R 2 are as defined above, with an acid-halogenating agent or an active esterifying agent to obtain a reaction product; and (ii) reacting the reaction product with an alcohol derivative having tne formula, HO-A wherein A is as defined above; a method for producing the pyri,-idine derivative (1) which.comprises reacting a carboxylic acid derivative .having the formula 0

CO*

y3 II R2 10 wherein X, Z, Y, y2, y3, R1 and R2 are as defined above, with a halide having the formula, yl N 10 wherein X Z, YJ, Y2, y3, Ri and R 2 are as defined above, with a halide having the formula, 3 -A (7) wherein A is as defined above, and W 3 is halogen; a compound having the formula, 0 y3 U

COA

2 (2) y2 X yl wherein A, X, Z, Y1, Y2 and Y3 are as defined above; a herbicidal composition which comprises as an active ingredient a herbicidally effective amount of the pyrimidine derivative described above, and an inert carrier or a diluent; a method for controlling undesirable weeds, which comprises applying the above herbicidal composition to an area where undesirable weeds grow or are likely to grow; and a use of the pyrimidine derivative as a herbicide.

In the compound of the formula the substituents R 1 and *o

R

2 which may be the same or different, are preferably C 1 .9

C

6 alkoxy, and more preferably, both of them are methoxy.

A is preferably a C 3

-C

5 dioxacycloalkyl alkyl group.

S• More preferably, A is 1,3-dioxolane-2-yl 9.

C-C, alkyl group or 1,3-dioxan-2-yl C 1

-C

6 alkyl group.

S, Most preferably, A is 1,3-dioxolane-2-yl ethyl group or 1,3-dioxan-2-yl ethyl group.

X is preferably oxygen.

b Z is preferably nitrogen or CY 5 wherein Y 5 is hydrogen or halogen, a halo alkyl group, a C.-C 6 alkyl group, a 8 CI-C, alkoxy group or a substituted or unsubstituted phenyl group. More preferably, Z is nitrogen or CY 5 in which Ys i3 hydrogen or halogen. Most preferably, Z is CY 5 and Y is halogen.

Y1 and Y2, which Inriy be the same or different, are preferably a hydrogen atom or a fluorine atom.

Y

3 is preferably hydrogen, fluorine or a C 1

-C

6 alkoxy group.

The pyrimidine derivative can also be produced by reacting a compound represented by the formula 0

I

y3 Z COH y2R (4)

R

1 Y1

N

20 N *0 wherein R 1

R

2 X, Y Y2 Y3 and Z are as defined above, with an acid-halogenating agent or an active esterifying agent (hereinafter reaction and reacting the resulting reaction product with an alcohol derivative represented by the formula 00 3 0* se 0 6 0.0- EO-A 1 wherein A is as defined above (hereinafter reaction (ii) In the above reaction specific examples of the acid-halogenating agent are thionyl chloride, thionyl brom~ide, phosphorus trichioride, phosphorus tribromide, phosphorus pentachioride, phosphorus oxychioride, phosgene, oxalic acid dichloride, etc.

Specific examples of the active, esterifying agent are N,NI-disubstituted carbodiimides such as N,N'dic-yclohexyicarbodiimide, N,N'-diisopropylcarbodiimide, l-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, etc.; arylsulfonyl chlorides such as o 2,4,6-trimethylbenzenesulfonyl chloride, 2,4,6- 9. triisopropylbenzenesulfonyi chloride, etc.; N,N'- S 0: 15 carbonyldiimidazoie; Iiphenylphosphorylazide; Nethoxycarbonyl-2-ethoxy-l, 2-dihydroquinoline; N-ethyl- 21-hydroxybenzisoxazolium trifluoroborate; phenylisoxazolium-3 '-sulfonate; etc.

By this reaction, a compoLnd represented by :20 the formula ooy3 z ~C-W2 y2

RI

Y1

N

N

R

1wherein R1, R 2 X, yl, y2, y3 and Z are as defined above, is producedi in the reaction system.

In the above formula a substituent W2 represents a halogen atom when the acid-halogenating agent was used; W2 represents an N,N'-disubstituted-2isoureido group when N,N'-disubstituted carbodiimide was used as the active esterifying agent; W2 represents an arylsulfonyloxy group when arylsulfonyl chloride was used as said agent; W2 represents an imidazolyl group when N,NI-carbonyldiimidazole was used as said agent; W2 represents an azide group when diphenyiphosphorylazide was used as said agent; W2 represents an ethoxycarbonyloxy group when N-ethoxycarbonyl-2-ethoxy-1, 2dihydroquinoline .was used as said agent; W2 represents a 15 3-(N-ethylaminocarbonyl)-2-hydroxyphenoxy group when Nethyl-2 '-hydroxybenzisoxazoi.um trifluoroborate was used as said agent; and W2 represents a group _1 _S03

E)

9* 9 9.

.9 99 99 U 9 999999 9 9. 9 99 .9 *9 9 9 99 9 9 9**9 .9 9. 9 *..999 9 .9 99 9 9 9 20 when H "IICONHC2H 3'-sulfonate was used as said agent.

In the reaction system, W2 can also take a form of acid anhydride containing the moiety represented by the formula, 0 y3 Z COy2

R

1 yli N N R2 1 wherein R1, R 2 X, yl, y2, Z3 and Z are as defined above.

The amount of the foregoing acid-halogenating agent or active esterifying agent used is usually 1 to equivalents based on 1 equivalent of the compound represented by he formula The amount of the alcohol derivative of the formula used.is usually 1 to 5 equivalents based on 1 equivalent of the compound represented by the formula S 6 10 The reactions and (ii) can also be carried out, if necessary, in the presence of a base.. Such a base includes organic bases 1-methylimidazole, 3nitro-lH-l,2,4-triazole, 1H-tetrazole, IH-1,2,4triazole, imidazole, pyridine, triethylamine) and 15 inorganic bases potassium carbonate). The amount of the base used is usually 1 to 20 equivalents based on 1 equivalent of the compound represented by the formula The reactions and (ii) are usually carried out in the presence of an inert solvent. Such a solvent includes aliphatic hydrocarbons hexane, heptane, 1 ligroin, petroleum ether), aromatic hydrocarbons (e.g.

benzene, toluene, xylene), halogenated hydrocarbons chloroform, carbon tetrachloride, dichloroethane, chlbrobenzene, dichlorobenzene), ethers diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g.

.acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters ethyl formate, ethyl acetate, butyl acetate), nitro compounds (e.g.

nitroethane, nitrobenzene), nitriles acetonitrile, isobutyronitrile), tertiary amines pyridine, triethylamine, N,N-diethylaniline, tributylamine, Nmethylmorpholine), acid amides N,N-dimethylformamide), sulfur compounds dimethyl sulfoxide, 15 sulfolane) and the mixtures thereof.

o Generally, the reaction temperature usually

S

ranges from 0 C to the boiling point of the solvent in *5 any of the reactions and The reaction time usually ranges from 1 to 24 hours for each reaction, and 20 from about 1 to about 48 hours through the reactions (i) and (ii).

After completion of the reaction, the reaction A:ee solution may be after-treated as usual. That is, water is added to the solution which is then extracted with an 25 organic solvent and concentrated, and if necessary, the product obtained is subjected to The chromatography, distillation, recrystallization, etc. Thus, the desired compound-can be obtained.

13 THE PRESENT INVENTION The present invention provides a compound having the formula,

O

y3 D

COA

y2 X (2) yl wherein A is C 3

-C

6 oxacycloalkyl, C 3

-C

6 oxacycloalkyl substituted with at least one member selected from the group consisting of CI-C 6 alkyl and halogen, C 3

-C

6 oxacycloalkyl C 1

-C

6 alkyl, C 3

-C

6 oxacycloalkyl C 1

-C

6 alkyl substituted with at least one member selected from the group consisting of C 1

-C

6 alkyl and halogen, C 3

-C

dioxacycloalkyl, C 3 -Cs dioxacycloalkyl substituted with at least one member selected from the group consisting of C i

C

6 alkyl and halogen, C3-C 5 dioxacycloalkyl C 1

-C

6 alkyl or

C

3

-C

5 dioxacycloalkyl C 1

-C

6 alkyl substituted with at least S• one member selected from the group consisting of C,-C 6 alkyl and halogen; X is oxygen or sulfur; Z is CY 4 each of Y Y 2 and Y 3 which may be the same or different, is hydrogen, halogen, Cl-C 6 alkyl or C,-C 6 alkoxy.

i 0 20 PA, b of3 yl v2 -An 3 T. 3 a b ':CZ3 :Cdhip 4fr'.se a_ Y4 is hydrogen, hydroxyl, mercapto, nitro, halogen, CI-C 6 alkyl, C 2

-C

6 alkenyl, C 2

-C

6 alkynyl, C 1

-C

6 alkoxy, C3-C 6 alkenyloxy, C 3

-C

6 alkynyloxy, halo Ci-C 6 alkyl, halo C 2

-C

6 14 alkenyl, halo C 2 alkynyl, halo alkoxy, halo C 3

-C

alkenyloxy, halo C 3 alkynyloxy, C 1 alkoxy C 1 alkyl,

C

3 alkenyloxy C 1 alkyl, C 3 alkynyloxy alkyl, cyano, formyl, carboxyl, C 1 alkoxycarbonyl, C 3

-C,

alkenyloxycarbonyl, C 3 alkynyloxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of alkyl, C 1 alkoxy, halo C 1 alkyl, C 1 alkoxycarbonyl and halogen, phenoxy, phenoxy substituted with at least one member selected from the group consisting of C 1 alkyl, alkoxy, halo C 1 C, alkyl, alkoxycarbonyl and halogen, phenylthio, phenylthio substituted with at least one member selected from the group consisting of C 1 alkyl, C 1 alkoxy, halo

C

1 alkyl, C 1 alkoxycarbonyl and halogen, benzyloxy, benzyloxy substituted with at least one member selected from the group consisting of C 1 alkyl, CI-C, alkoxy, halo

C

1 alkyl, CI-Cs alkoxycarbonyl and halogen, benzylthio, benzylthio substituted with at least one member selected from the group consisting of alkyl, CI-C, alkoxy, halo 99 99 alkyl, C 1 alkoxycarbonyl and halogen, 999999 **9

RS

-N

R6 S wherein each of R and which may be the same or different, is hydrogen, C.-C 6 alkyl, C 3 alkenyl or C3-C, alkynyl, .:fee: 4

O

1 R- 9. C N

R

6 wherein RS and R are as defined above, in wherein R 7 is C3.-C 6 alkyl, C 3

-C

6 alkenyl or C 3

-C

6 alk-ynyl and m. is an integer of 0, 1 or 2, _X1 -C--7 wherein X 1 is oxygen or sulfur, and R 7 is as defined above or

-(-CH

2 S R 7 4

S

S. S o 5* *5 *5

S

*S *S S S S S *5 *5

S

S.

0S o 5

S

*5*S

S

*55@ (Ohs wherein R 7 and m. are as defined above, and n is an integer of from 1 to 4..

The compound of the present invention represented by the formula can be produced by reacting an aromatic carboxylic acid derivative represented by the formula coH (9) wherein X, Y Y Y 3 and Z are as defined above, with an acid-halogenating agent or an active esterifying agent (hereinafter reaction (iii), and reacting the resultingr reaction product with the alcohol derivative represented by the formula (hereinafter reaction 16 The above reactions (iii) and (iv) can be carried out according to the foregoing reactions and (ii), respectively.

The aromatic carboxylic acid derivative can be produced according to J. Org. Chem., 27, 3551 (1962), Chem. Pharm.

Bull., 31, 407 (1983), Yakugaku Zasshi, 99, 657 (1979), Chem. Pharm. Bull., 27, 1468 (1979), J. Med. Chem., 21, 1093 (1978), Yakugaku Zasshi, 92, 1386 (1972), Eur. J. Med.

Chem-Chim. Ther., 21, 379 (1986), J. Chem. Soc., Perkin Trans. 1, 2069 (1979), J. Chem. Soc., Perkin Trans. 1, 2079 (1979), J. Chem. Soc., Chem. Commun., 1127 (1968), J. Med.

Chem., 31, 1039 (1988), Indian J. Chem., 25B, 796 (1986), J. Am. Chem. Soc., 107, 4593 (1985), J. Org. Chem., 50, 718 (1985), J. Agric. Food Chem., 32, 747 (1984), J. Pharm.

Pharmacol., 35, 718 (1983), J. Org. Chem., 48, 1935 (1983), J. Chem. Soc., Chem. Commun., 1974 362, etc.

S: Compound includes its stereo isomers.

Production Examples for the compound are shown below.

S

6 Production Examples 9.00 Grams of acetylasalycilic acid and 9.95 g of 2-(2bromoethyl)-1,3-dioxane were dissolved in 1-00 ml of N,Ndimethylformamide was mixed with 7.60 g of anhydrous potassium carbonate. The resulting solution was stirred at 0..

120°C to 130°C for 3 hours. The reaction solution was 25 poured into diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer separated from the a aqueous layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The

S

solvent was removed under reduced pressure, and the residue obtained was distilled under reduced pressure to obtain 10.5 g of 2-(1,3-dioxan-2-yl)ethyl salycilate in yield of 83%.

17 N 24

D

12OOC-.122OC/O.O7 mmHg 1. 5246 Table 2 illustrates specific examples of the compound which can be produced by using the corresponding starting materials.

Tabt&F 2 o *0 *5 S S

OS

S

0 0**SSS

S

5o55

S

*SSS

0 0 -0-A Y2- XH

YI

A Y' Y 2 3 1X z 0 H H tA\0 CF Cont'd Table 2 (cont'd)

A

0~

Y

1

H

H

y2

H

H

Y

3

H

H

x 0 0 z CCl

CH

c' CBr 1 I 0- H IH I

S

0 0- H H H 0 0 00 0 0a 0 .00 .0.0* H H H S CBr H H H 0 GOGH 3 0 H H H 0 CCI 0C H H H 0 CCI 0C H H H 0 CF H H H 0 CCF 3 -Cont'd Table 2 (cori'd) A y 1 2 y3fx z H H H 0 CCH 3 -0 H H H 0 CC 6

H

0H H H 0 CN0 2 H H H o cc[ C2H H H 0 1

CF

09 0 H H1 H 000H 992 90 Cont'd Table 2 (cont'd) A y1y2Yjx z 0jY C2H H H 0 CCI C2H H H 0 CH C2H H H 0 CCF 3

CH

2

CH

2

CH

2 -Q5 H H H 0 CGSCH 3 0

CH

2

CH

2 H H H 0 CC2HS

(CH

2 H H H 0 G' N 2

CH

2 0 H H H 0 CNO 2

OH

3

::CH

2 H H H 0OCOCH 3 0

H

3 C

H

3 H H H 0

O

H OO 0 foo 0 -Cont'd Table 2 t otd A y y 3 x Z 0 H CH 3 H 0 CC[ 0 0 )H H F 0 CBr 0 )o *C 2 Hs H H S CB,3 0 0 H Cl H 0OCOCH 3 .0 )c H H F 0 CCF 3 5.55.5 I0, 0C O H H 0 CCI 0 CH3 C3 H H H 0 CF 0H H H 0 CH Se 0O H H H H S C C 000.0 0

CH

3 0 C 3Cl H H 0 CBr x- C11

L

0

CH

3 Table 2 (con~d) C C

C.

C. CC C CC

CC

C. A y 1 y 2 y 3 x z -C0CH 3 H H H SCBr OC 2 1 5 H H H 0OCOCH 3 0 H5H H H 0 CCI o 0 3 H<2,1 7 (n) CHC2-<H H H 0 OH 0

CH

2

CH

2 H H H 0 OH 0 0

CH

2 H H H 0 CCr 0 CH3 IH H 0+-K H H 0 CCH 3

OH

2 Hl H H 0 OHr Ae Cont'd Table 2 (cont'd) A y I y 2 y 3 x z

CH

2 CH H F1 0 CHI

OH

2

CH

2 D H H F 0 OH 0HC 2 K iH0O 0 0

CH

2

H

2 -KIDJ H OH3 0 OH 0 o

OH

2

H

2 H 01 H 0 OH 00 a o *0 0* 00 0 0

OH

2

H

2 H OH 3

CH

Cont'd Table 2 (cont'd) 0* 4 4 4* .44444 *4*4 Cont'd

('I

Table 2 (cort'd) A y I y 2

CH

2

CH

2 H H o

CH

2

CH

2 H H o

CH

2

CH

2 H H 0

H

2 0H 2 H H 0

:*CH

2

CH

2 H H 0

CHCH

2 *4 0

CH

2

CH

2 H H

CH

2

CH

2 H Cont'd Table 2 (gontcl) S S OS 0 000000

S

Cont'd Table 2 (cont'd)

A

0

CH-

2

CH

2 (0I< 0

C

2

OH

2 -(13 o CH 3

CH

2

CH

2 T 0 H 3

CH

2

CH

2 0. GH 3

C

3

H

7 (n)

CH

2

CH

2 0 {-0H 3 0

CH

2

C

2 OXH 3 0 0

OH

3

CH

2

CH

2

OH

3 CH CH 2

C

2 1- 5

OH

3

CH-

2

CH

2 -K7-< Li1y H H

HH

H H H H H H H H H H H H H H H H Y 3

H

H

H

H

H

H

H

H

H

x 0 0 0 0 0

S

0

S

0 z cl

CI

*C

2 1- Ci IC 2 1ccI

CF

ci

GOC'

CBr CBr

GOGH

3

CCI

S. S

S.

5* S S S. S S S

S

HI10 /1 This application is divided from application 33971/93 and thLe entire disclosure in the specification of the said application 33971/93 is by this cross-reference incorporated into the present specification.

It will be clearly understood that the invention in its general aspects is not limited to the specific details referred to hereinabove.

A

OS

S

S

*e *o

Claims (8)

1. A compound having the formula, 0 Z C-O-A (2) y1 wherein A is C 3 oxacycloalkyl, C 3 -C 6 oxacycloalkyl substituted with at least one member selected from the group consisting of C3-C, alkyl and halogen, C 3 -C 6 oxacycloalkyl Ci-C 6 alkyl, C 3 -C 6 oxacycloalkyl Ci-C 6 alkyl S• substituted with at least one member selected from the group consisting of Ci-C 6 alkyl and halogen, C 3 -C dioxacycloalkyl, C3-C 5 dioxacycloalkyl substituted with at S, least one member selected from the group consisting of C i C 6 alkyl and halogen, C 3 -C 5 dioxacycloalkyl C 1 -C 6 alkyl or C 3 -Cs dioxacycloalkyl Ci-C 6 alkyl substituted with at least one member selected from the group consisting of Ci-C 6 alkyl and halogen; X is oxygen or sulfur; Z is CY 4 each of y 1 Y 2 and Y 3 which may be the same or different, is hydrogen, halogen, Ci-C 6 alkyl or Ci-C, alkoxy; and Y 4 is hydrogen, hydroxyl, mercapto, nitro, halogen, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halo Ci-C 6 alkyl, halo C 2 -C 6 alkenyl, halo C 2 alkynyl, halo CI-C 6 alkoxy, halo C.-C. alkenyloxy, halo C 3 alkynyloxy, C 1 alkoxy C 1 -C6 alkyl, C 3 alkenyloxy C 1 -C 6 alkyl, C 3 alkynyloxy alkyl, qyano, formyl, carboxyl, C 1 alkoxycarbonyl, C 3 -C. alkenyloxycarbonyl, C 3 alkynyloxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of C 1 -C alkyl, alkoxy, halo C 1 alkyl, alkoxycarbonyl and halogen, phenoxy, phenoxy substituted with at least one member selected from the group consisting of C 1 -C alkyl, CI-C, alkoxy, halo C 1 C. alkyl, C 1 -C 6 alkoxycarbonyl and halogen, phenylthio, phenylthio substituted with at least one member selected from the group consisting of C,-C 6 alkyl, C 1 alkoxy, halo alkyl, alkoxycarbonyl and halogen, benzyloxy, beinzyloxy substituted with at least one member selected from the group consisting of CL-C, alkyl, C 1 alkoxy, halo C-C 6 alkyl, C 1 -c 6 alkoxycarbonyl and halogen, benzylthio, benzylthio substituted with at least one member selected *00000 from the group*consisting of C 1 -C alkyl, C1-C 6 alkoxy, halo CI-C, alkyl, C-C. alkoxycarbonyl and halogen, R6 wherein each of R 5 and R 6 which may be the same or 0*0*00 different, is hydrogen, C 1 alkyl, C 3 alkenyl or C 3 -C 6 alkynl, 0 11 I R -C-N wherein R 5 and R 6 are as defined above, S R 7 11 M wherein R 7 is C 1 alkyl, C 3 -C, 6 alkeny. or C 3 alkynyl and m is an integer of 0, 1 or 2, 0 -X:i -C-R7 wherein X 1 is oxygen or sulfur, and R* 7 is as def ined above; or 4 9* 0* 55 S C C C *9*CCC V C. S a ,s 5* C* V a C 0* V C C C 55 0O C C sea. C S.C. ~CH~j--S -R 7 (0)m wherein R 7 and m are as defined above, and n is anu integer of from 1 to 4.

2. A compound according to Claim 1, wherein A is C3- CS dioxyacycloalkyl alkyl.

3. A compound according to Claim 2, wherein A is (l,3-dioxolane-2-yl) alkyl or (1,3-dioxan-2-yl) CI,-CG alkyl.

4. A compound according to Claim 3, wherein A is 3 -dioxo lane -2 -yl) ethyl or 3-dioxan-2-yl) ethyl- A compound according to Claim 1, wherein X is oxygen.

6. A compound according to Claim 1, wherein Z is CY wherein Y 5 is hydrogen, halogen, halo C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenyl or phenyl substituted with at least one member selected from the group consisting of C 1 C, alkyl, Cl-C 6 alkoxy, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl and halogen.

7. A compound according to Claim 3, wherein Z is CH, CF, CC1, CBr or CI.

8. A compound according to Claim 1, wherein both Y 1 and Y 2 are hydrogen or fluorine, and Y 3 is hydrogen, fluorine or C 1 -C 6 alkoxy.

9. A method for producing a compound of formula (2) as defined in claim 1, substantially as hereinbefore 15 described. DATED THIS3rd DAY OFDecember 1993 SUMITOMO CHEMICAL COMPANY, LIMITED By its Patent Attorneys: GRIFFITH HACK CO 20 Fellows Institute of Patent Attorneys of Australia. o S S 0 *5*o S 550o ABSTRACT An intermediate of formula useful in the preparation of pyrimidine derivatives having herbicidal activity the subject of applicant's earlier application 76467/91, is disclosed and claimed, in which the substituents A, X, Y, y2, y3 and Z are as defined in the specification.