JPS6289680A - Herbicidal imidazole, pyrazole, thiazole and isothiazole derivatives - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel N-[(polycyclic) ami7carponylj
Relates to imiguzole sulfonamides, pyrazole sulfonamides FM, thiazole sulfonamides and isothiazole sulfonamides, herbicide compositions containing them and methods of using them to control undesirable plant growth. It is something.

There is a continuing need for new compounds that are effective in controlling undesirable plant growth. In the most common circumstances,
Such compounds are sought for selectively controlling the growth of weeds in useful crops such as cotton, rice, maize, wheat and divers. Uncontrolled weed growth in such crops results in substantial losses, reducing farmers' profits and increasing costs to consumers. In other situations, herbicides that inhibit the growth of all plants are desired. Examples of areas where complete suppression of all plants is required are locations around fuel storage tanks, ammunition tanks and industrial storage areas. Although there are many products commercially available for these purposes, research continues into more effective, less expensive, and environmentally safe products.

Various types of N-[(heterocyclic)-aminocarbonylcoaryl sulfonamides are known as herbicides.

The two earliest patents issued for such compounds were October 2, 1979 and October 19, 1979, respectively.
U.S. Pat. No. 4,169, issued II/288/78.
719 and 4,127,405. These patents contain a general formula [wherein W can be 0 or S, 2 can be N or CH, and R is optionally substituted benzene, optionally substituted which may be optionally substituted thiophene, optionally substituted furan or naphthalene. What about the subsequent literature?

For example, European patent application 812302461.9.1, published December 9, 1981, discloses similar compounds in which R is thiophene or pyrrole.
82301500 issued on November 17, 982.
3. 803042 issued June 101, 1981]
87.8.8130 issued November 4H, 1981
1874.

4 Sanyo. In this document, N-[(heterocyclic)amine carbonylcoimitazole-, pyrazole-.

There was no disclosure of thiazole- or isothiazole sulfonamides or indication that the new compounds were useful as herbicides.

It has now been found that compounds of formula I have utility as plant growth inhibitors and/or Q removers.
0 Q-5O□NIICN-A゛ [wherein R is H or CH.

Q is R1゜ Q-7Q-s　　　　　　　-9 Yes.

R1 is H, 01-C8 alkyl, C3-C6 alkenyl, C6-C, cycloalkyl, 05-C6 cycloalkenyl, C3-C6 alkynyl, C4-C7 cycloalkylfurkyl, (Rt 7 CH) nC (0) Rt a,
(Rt ? CH) ncO2R1B, (R17CH) ncO3R1g, (Rt ? CH) ncONR2o R21, (R17
CH) nsO2NR2o R2+, (Rt 7 CH)
nsO2R22, a) 1 to 3 F, Br or CI atoms.

or b) C4-C substituted with OR,6.

is alkyl, R2, R3 and R4 are independently H or CH3, R6 is H, C1-C, alkyl, -0R6, NO2, F
, CI, B r, CO2R2,,S (0)mR2! l
or SO2NR2o R2l, R6 is H, C, -C4 alkyl, 03-C.

Alkenyl, 03-C4 alkynyl, CO2R1a, 5O2NR2o R2□, S○2R2
2 or a) 1 to 3 F, CI or Br atoms, or b) C1 to C4 alkyl substituted with OCH3, R7 is H or CH3, R8 is H, C, ~C4 alkyl, - O R,,,No□,F,C1,Br,CO2R24,S
(0) mR2s or 5O2NR2°R21, R9 is CH3 or C, H, RIO is H, C1-C, alkyl, C3-C, alkenyl, C3-C4 alkynyl, C02R24・SO2NR
2o R2t or 5O2R22, R□1 is H, C, ~C3 alkyl, F.

C1,Br,NO2,-OR,,,CO2R24,S
(0) ml'12 g or 502 NR2o R
2t Te, R12 is H or CH3, R13 and R14 are independently H, C, -C, alkyl, -OR, 6, F, CI, Br, NO2, CO2
R24, S (0) mR25 or Sot NR2o
There is R2r Te.

R15 is H or CH3; R16 is C1-C3 alkyl; is C, ~C47/lzki/lz, C3-C4 fluorenyl, C3-C4 alkenyl or CH2CHy O
CH3't', R20 and R21 are independently CH3 or C2H, R27 is C, -C3 alkyl or CF3, R23 is H, C1, Br, CH3, F, CFi, OCH
3 or No2-c, R24 is C1-C3 alkyl or allyl, R45, is C1-C3 alkyl, O is Oll or 2, n is O or 1, R2g is H, C, ~c3 alkyl or CH2O(0)
NH and R? 7 is H, C, -C3 full*, c1-C3 alkoxy, 01-C3 alkylthio or C2-C3 alkoxycarbonyl, R261±H, C, -C, 7Jlzkyl, cI-C3 alkoxy, 01-C3 Alkylthio, C1-C3 alkoxycarbonylC1. Br or CF3.

R29 is H. Cl or CH3.

R30 is H. Cl or CH3, and R31 is C1.
C,~C,7rukoxycarbonyl A is A-I A-2 A
-3A-4A-5, and X is CH3, OCHi, Cl, F.

0CF2H or 5CF2H, Y is CH3, Ct Hs, OCH3,0C7Hs,
CH20CH3, CH(OCH3)2.0CH2CF3.0CF3, NR
2, NHCH3, N(CHi)2 or GCF2T, where G is 0
or S and T is HlCHCIF, CHBr
F, CF2H or CHFCF, 2 is CH or N, Yl is H, C1, CH3, OCH3 or 0CF2H, x2 is OCH3, CHt, CH2CH3.

SCH, or 5CH2CH3, and Y2 is CHa
, CH2CH3 or CH2CF, and X s If OCH3i tit CHs theari,
However, as a condition.

a) When Q is Q-7, Q-8, Q-9 or Q-1O, R is H; b) the total number of carbon atoms in R is 8 or less; c) R is C
If other than 1"C3 alkyl, R3 must be H, d) When R, is other than H, CHa, OCH3"E or NO2, R6 is H or CH, e) R6 is C02R,... S 02 NR2o R2s Mall':1tsO2R
When there is 22 Te, R, is H, CHa, OCH3;
: Or NO2.

f) When R+ o is other than C1-C3 alkyl,
RIL is H, CI, OCH, No2 or CH.

g) One of Rr a or R14 is CO2R24, S (0) mR25 or SO2NR2
a When R2t, the other is H, CI, CHI,
OCH3 or NO2; h) R2s and R30 are not C1 at the same time; i) when x is CI or F, Z is CH;
and Y is OCH3, NR2, NHCH3 or N(C
H3) 2 and i) when Q is Q-7, Q-8, Q-9 or Q-10, A is A-1 and X is CH
,,OCH3 or 0CF2H.

Y is CH3, OCH:1. and k) when X or Y is 0CF2H, Z is CH] and agriculturally suitable salts thereof.

Accordingly, the present invention relates to compounds of formula I, herbicidal compositions containing the compounds, and methods of using the compounds to control undesirable plant growth.

A group of compounds are characterized by their high herbicidal activity and/or
Or plant life 111! They are preferred because of their activity and/or because of their ease of preparation. These preferred groups are shown below: 1. Q is Q-1, R is H, formula 1% la, A is A-1'r, and Z is CH Preferred compounds of ■, which have 't'.

ib, x is CH3, C1, OCH3!7', 1toCF
, H, and I, CY is CH,, OCH3 or 0C
It is F2H. Preferred Compounds of Ia.

Suitable Ta compounds, wherein 1c, R, is H or C1-C4 alkyl, and R3 is H.

2, Q is Q-2, R is H, Formula 1% 2a, A is A-1, Z is CH, R4
is H. Two preferred compounds.

2b, X is C) I3. CI, OCH3 or 0CF2H
and Y is CH3, OCH3 or 0CF2H
Preferred compounds of 2a are:

2c, R, is H, CH3,0CHs, CI, NO2,
Preferred compounds of 2b are CO2R24 or SO2NR2o R2I and R6 is H or C1-C4 alkyl.

3, Q is Q-3, R is H, formula 1% 3a, A is A-, l, Z is CH, and R is H. 3 preferred compounds.

3b, Preferred compounds of 3a, wherein X is CH3, CI, OCH3 or OCF, H and Y is CH3, OCH3 or OCF2H.

3c, Re is B r, C+ ~Ca alkyl, OCH3
, C1, NO2, CO2R24S (0)mR25 or SO2NR2o R2t. Preferred compounds of 3b.

4. Preferred compounds of formula 4, wherein Q is Q-4, R is H, formula 1% 4a, A is A-IC', and 2 is CH.

4b, X is CHa, Cl, OCH3 or OCF,
H, and Y is CH,,OCH.

or 0CF2H. Preferred compounds of 4a.

4c, Rlo is H, C, -C, alkyl, CO2CH3
,5o2CH3 or S 02 N (CHI ) 2 and R11
is H, CHa, QC) I3, C1, Br, NO2,
C02CHs, S02CH3 mata is SO2N (
Preferred compounds of 4b are CHi )2.

5, Q is Q-5, and R is H, Formula 1% 5a, A is A-1, and Z is CH. 5 preferred compounds.

5b, X is CH3, C1, OCH, or 0CF2H and Y is CHs, OCH3 or 0CF2
Preferred compounds of 5a are H.

5c, R++ is H, CH3, OCH3, Cl.

Br, NO2, Co2CH,,5o2CH, or SO
□N(CHz)2. Preferred compounds of 5b.

6, Q is Q-6, and R is H, Formula 1 % 6a, A is A-1, and Z is CH. 6 preferred compounds.

6b, X is CH3, CI, OCR, or OCF, H and Y is CH3, OCH.

or 0CF2H. Preferred compounds of 6a.

6c, R, and R14 are independently -1(H, CH3,
0CHz, C1, Br, NO2, CO2CH3, S
O2CH3 or 302N(CH3)2.

Preferred compounds of 6b.

7. Compounds of formula I, wherein Q is Q-7, Q-8, Q-9 or Q-1°, and Z is CH.

7a, R2O is H when Q is Q-9. 7 compounds that are closely related.

7b, Q is Q-7, Q-8 or Q-1o. 7 preferred compounds.

7c, Q is Q-7, R26 is H or CH3, and R27 is H, CH3, C.

Preferred compounds of 7b are C2 alkoxy or C,-C2 alkoxycarbonyl.

7d, Q is Q-10 and R31 is Co2CH
Preferred compounds of 7b are 3.

The following compounds are particularly preferred because of their high herbicidal activity and/or plant growth 2g1 nodal activity and/or their ease of synthesis.

N-4(4,6-dimethylpyrimidin-2-yl)ami7carponyl)-LH-imidazole-2-sulfonamide, melting point 185-186°C (d), N-[(4-methoxy-6-methyl (pyrimidin-2-yl)aminocarbonylruethyl)-18-imidazole-2-sulfonamide, melting point 157-158°C (d), N-[(4.6-cymethoxypyrimidin-2-yl)aminocarbonyl] -
1-(1-methylethyl)-1H-imidazole-2
-Sulfonamide, melting point 166-167°C, N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-ethyl-lH-imidazole-2
-Sulfonamide, melting point 196-197°C, N-((4-methoxy-6-methylpyrimidin-2-yl)aminecarbonyl]-1-ethyl-lH-imigun-2-sulfonamide, melting point 178-179°C (d
), N-[(4.6-Simethoxypyrimidin-2-yl)aminocarbonyl]-1-ethyl-IH-iminozole-
2-sulfonhumide, melting point 186-187°C, N-((4,6-cymethoxypyrimidin-2-yl)ami7carponyl-IH-imidazole-4-sulfonamide, melting point 2)
05-206°C, N-[(4-methoxy-6-methylpyrimidin-2-yl)aminecarbonyl]-4-thiazolesulfonamide, mp 196-200°C (d).

N-[(4.6-Simethoxypyrimidin-2-yl)aminecarbonyl]-4-thiazolesulfonamide, melting point 201-203°C, N-[r(4-methoxy-6-methylpyrimidin-2-yl) ami7carponylcoaminosulfonyl]-
Methyl 3-inchazolecarboxylate, fused □. j1
28°C (d), and 4C[(4.6-
Methyl cymethoxypyrimicin-2-r)aminecarbonyl 3-isothiazolecarboxylate, melting point 161°C (
, l).

Intervention a. 1. The sulfonylureas of the invention can be obtained by a number of methods.
These methods and the literature or S'H4 that describe them are as follows. (a) is reacted with a suitable amino heterocycle (b). The reaction is corrosion-resistant carried out in an inert solvent such as methylene chloride, tetrahydrofuran, ayatonitrile, ether or chloroform at a temperature within the range of about -20 to 50°C. In some cases,
The desired products can also be crystallized from the reaction medium and filtered. Reaction products that are soluble in the reaction medium can be liberated by evaporating the solvent and trituring the residue with a solvent such as diethyl ether, ethyl acetate, l-chlorobutane or hexane.
Chromatography (eg silica gel) is also required for purification. This method is patented in 7th National Patent No. 4,127,405,
4,257.802 and 4,221,585.
has been completed.

Reaction, Formula 1 % Formula % Qso2NH-C-tv-yt As shown in Reaction Scheme 2, compounds of Formula 1 (1) are prepared by reacting the sulfonamide (a) in the presence of equimolar acid trimenal aluminum. It can also be produced by reacting with methyl cartamate.

The reaction is carried out in an inert solvent such as methylene chloride, with a width of about 25
Best carried out under a nitrogen atmosphere at ~40°C for 10-96 hours. Products can be isolated by adding aqueous acetic acid and subsequently extracting the product in methylene chloride, or by filtering products of low solubility, such as 1-chlorobutane, ethyl acetate or ethyl ether. By trituring with a solvent,
or by column chromatography on silica gel.
The product can be purified.

Reaction Scheme 3 %Formula % ] Examples of other methods of preparing the compounds of the invention are illustrated in Reaction Schemes 3 and 4, which were published in June 1981 at lO8
European patent application 80304285.2 published in
It is written inside. The first step of this two-step process (Scheme 3) is N-(halo double J Lm aminocarbonyl)-
It involves the reaction of a diazole sulfonamide with a heterocyclic incyanate to produce the aromatic sulfonamide I.(f). The reaction is best carried out in an inert organic solvent such as acetonitrile, tetrahydrofuran, toluene, acetone or butanone, preferably at a temperature of about 25 DEG to 110 DEG C. The product is then further reacted with selected nucleophiles, such as alkoxide-OR' (Scheme 4).

The herbicidal N-(substituted heterocyclic amine sulfonyl) aromatic sulfonamides of the present invention are produced.

(C) (g) European patent application 81810282 published on January 27, 1982 17127 H. .4゜Schemes 5 and 6 illustrate two other methods of preparing compounds of the invention.1 As shown in Scheme 5, siasolsulfonamide Ce) is prepared in the presence of a base. React with N-heterocyclic rubbermate (h). On the other hand, in Reaction Scheme 1 6, N-phenylsulfonyl calhemate (h) is reacted with amine (b). Both of these methods are covered by European Patent Application No. 81810281.6 (Publication No. 4
4.807. January 1982, 270). Both reactions are best carried out in non-polar inert organic solvents such as methylene, tetrahydrofuran, acetonitrile, dioxane and toluene at temperatures between -20 and 120°C. Bases suitable for use in include organic bases such as amines, and inorganic salts such as hydrides, hydroxides, carbonates and bicarbonates.

Q is Q-1, R1 is as defined above, but n must be l, and R, R2
, R, and A, as defined above, are best prepared by the methods of Scheme 2.5 or 6.

Q is Q-2, Q-3, Q-4, Q-5 or Q-6, m is O or 2, and all other substituents are as defined above Compounds of I can best be prepared by the method of Scheme 2.5 or 6. Many of these compounds can also be prepared by -
The corresponding sulfide (m
It can be produced by oxidizing = O) with m-chloroperbenzoic acid.

Q is Q-7 or Q-8, and R211 is CH3C (
0) NH, and R27 and R28 are C8-C
Compounds of formula 1 other than 3 alkoxycarbonyl are 1
It can be best produced by the method of reaction formula 2.5 or 6.

Compounds of the present invention represented by formula 4 below (Q in formula I is Q-1 and R1 is (R+?CH)nc
OR+ a, (R17CH)ncO2R1@.

(R17CH)ncO5R1g, (R17CH)ncONR2o R2s, (R+
7 CH)nsO2NR2o R2r or (R
l 7 CH) n SO2R22 and R, R7, R, and A are as defined above) can be prepared by the method shown in Scheme 7 or 8.

Equation 7 Equation 8 B R In both Equations 7 and 8, Xa can be Ct, Br or I, and n is O and R, is C(0
)R+s, Xa can also be -0COR1*, and when n is O and R1 is -5O2R22
When , Xa can also be 105O2R22.

In Scheme 7, the sulfonylurea is dissolved in a suitable solvent such as CH2Cl2. The reaction mixture is reacted with a suitable alkylating or acylating agent, RIXa, in xylene or tetrahydrofuran for 1 to 50 days at temperatures between room temperature and the reflux temperature of the solvent, and the reaction mixture is poured into water; #Adan is neutralized to product 4 by reacting with an amount of base, such as Na2CO3 or Na2CO3. Isolating the product by extraction;
and then purified by conventional crystallization or chromatography techniques.

In Scheme 8, the sulfonylurea is reacted with 2 equivalents of a strong base 2, such as Na, in a suitable solvent, such as tetrahydrofuran.
Convert to its dianionic form using H, secondary butyl lithium or potassium tert-butoxide. The dianion is reacted with one equivalent of an alkylating or acylating agent, RIXa, to form the salt of A. The reaction mixture is poured into water and acidified to pH 2-3 using a mineral acid such as aqueous hydrochloric acid. Product 4
is isolated and purified as described in Scheme 7.

Heterocyclic amines of the formula (b) are described in U.S. Pat. No. 4,127.405, U.S. Pat. No. 4,221,585, Patent 001568
3 and European Patent Application No. 81303837.9 and South African Patent Application No. 1i8215045 published on March 3, 1982.

Heterocyclic carbamates of formula (d) are described in European Patent Application No. 83300073 published on January 6, 1983.
．． manufactured by the process taught in 0.

Sulfokolysocyanates are disclosed in U.S. Pat. No. 4,127.4.
Published on January 7, 1981! 1. f-yoo
It is also manufactured by the process taught in Patent Application No. 80301848.0.

Q is Q-1, R2 and R3 are as defined above, and R is H,C.

~C@alkyl, 04-C7 cycloalkylalkyl 1
1 to 3 F, Br or Ct atoms or 1 10
Sulfonamides of formula (C) that are 01-C6 alkyl substituted with R16, or are prepared by steps known in the art and set forth in Scheme 9.10 and IOa.

+
↑Mercaptoimidazoles 2 are known in the art. For typical processes, 'R, G, Jones, E, C, Kornfeld, C, Pine Chlorin (Mc
Laughlin and R.C. Anderson, J.Am.Chem.soc.
, 7 U. 4000 (1949) and the literature cited therein.

Mercabutimidanols 2 shown in Reaction Scheme 10
Methods for converting sulfone 7amides (c-1) are known in the art. For details, see R.O., Roblin.

Jr, and James W, -/C1app, J, Am, Chem, Sl.
L., 4890 (1950). Improved yields of sulfonamides are often obtained in this process when a chemically acceptable amount of 012 is used rather than in excess as described.

Q is Q-1, R2 and R3 are as defined above, and R1 is 03-C6 alkenyl,
C3-C6 alkynyl, COR+ s, CO2Rle
, C03R, , C0NR2°R2t , SO2NR2
Compounds of formula (C) which are °R21 or 5O2R2z are best prepared by the process of Scheme 11.

In the reaction R formula, Xa is C1 or Br; When R1 is C3-CS alkenyl or C3-C6 alkynyl, Xa may be I; When R, is COR, Xa is OCORla and when R1 is 5O2R22, Xa is 05OzR2
It may be 2.

This method is known to those skilled in the art and is carried out in a manner analogous to that described in Scheme 7.

Many of the sulfonamides of (C) are known in the art and can be prepared from known imidazole intermediates by chemical conversions known to those skilled in the art. General literature on the chemistry of imidazoles includes: Elderfield, Chemistry of Heterocyclic Compounds, Volume V, pp. 194-297, 1957
, Joan Wiley & Sons Incorporated, New York.

T., Kauffman and R.

Werthwein, Angew, C
hem,, Int, Ed, Engl, 1020-33 (
1971).

M, R, Grimmett, Ad
v, Heterocycle, Chem, 12.104~
184 (1970).

Substituted nitroimidazole sulfonamides of formulas (c-3) and (c-4) (Q is Q-2 or Q-3, and RS and Ro are -NO2) are prepared according to reaction scheme 12. Shown below.

During the ceremony.

R4 and R7 are H, R8 and R9 are H, CH3 or CH, C, R5, Xa is C1, Br or I, and R3 is CH3
Or CH, CH2.

This method was developed by B.S., Hua ng, and M.
, J., Lauzon and J.

C Parham, J, Het, Chem,
16.811 (1979). Using a similar process, structural formula (c-3
) can be produced by the intermediate products of R4 force (CH
, and also L to H, and R, is C2-C4 alkyl, C3-C4 alkenyl, C7-C4 alkyl substituted with 1 to 3 F, CI, Br atoms or 0CR3, Co2R,8, S02 NR+s R2゜or 5
Intermediates of structural formula (c-4), which are o2R2, can also be produced.

Bromo or chloroimidazole sulfonamides of formulas (c-5) and (c-6) (where Q is Q-2 or Q-3)
and R8 is Br or CI) is shown in Reaction Scheme 12a.

4(5) Production of bromoimidazole 1j is I.

E, Balaban and F, L.

Pyman, J, Chem, S.

c., 121.947 (1922). 4 (5) Promo 5 (4) Production of sulfonamidoimitazole↓1 Banne, L.
tt') and H,T, Baker,
J., Am., Chem., S.

C1, 79, 2188 (1956).

Methods for preparing other intermediates for use in the preparation of the compounds of this invention from readily available imidazole intermediates are shown in Scheme 1.

Clause ↑ and = 1.
, Soc, 121.947 (1922).

Protection of the imidazole nitrogen for subsequent processing of the ring is 1
For example CHs OCR2- or CHs OCHt C
This is carried out using groups such as H20-CH2-. These groups are C, Tang, D, Dav.
arian), P. Hua n g and R. Breslow, J. Am. Ch.
e.

Sac, 3918 (1978) and E, J + Corey, J, L, CraS and P, Ulrich, Tet, Let.
, 809 (1976).

Protection and deprotection by T. Brown
, G. Shaw and G. Duran.
ant), J, C, S, PerkinI2310 (1
The process taught in 980) can also be carried out using groups such as e.g.

Protection of the imidazole as described in Formula 1 gives a mixture of isomeric derivatives J and 20.

This mixture is used in the next step without separating the isomers, since deprotection of either isomer yields virtually the same product.

The addition of R5 or R8 such as F is described in U.S. Pat. No. 4,069.
262, in which chloronitrobenzene is converted to KF and C as catalysts.
Substitution with sF produces fluoronitrobenzene.

Halogen substitution in 11 and 20 to produce 22 and 22 in which R6 and R8 are =S (C-C3 alkyl) can be accomplished by halogen substitution using an appropriate mercaptide salt as shown in Scheme 1. Implemented by For details on halogen substitution by mercaptides in halonitroimidazoles, see L. L. Bannett.
nett) and H, T, Baker.

J, Am, Chem, Soc,, 79.2188 (19
56). Nitroalkylthioimidazole is oxidized so that R and R8 are -302 (C1 to C
Reference is also made to this same document for methods for preparing nitrofurkylsulfonylimidazoles of formulas 3 and 11, which are (3alkyl).

Compounds of formulas 22 and 22 in which R6 and R8 are -502NR2o R2I are prepared by oxidative chlorination of the corresponding thiol or benzyl mercaptide to the sulfonyl chloride.

Treatment of sulfonyl chloride with 2 equivalents of R2°R2,NH produces the desired intermediates. This process is shown in Process Formula 2.

The conditions for carrying out the conversion described in Scheme 2 are well known in the art, e.g., M, H.

Fisher, W.H., Nicholson and R.S.

Stuart, Can, J, Am, c
See hem, soc, E., 4890 (1950) and U.S. Pat. No. 4,310,346.

R6 and R9 are 0R06 and R16 is C1
Compounds of formulas and 22 that are ~C3 alkyl are prepared by replacing the halogen in and and 20 with the appropriate alkoxide. Suitable processes for the substitution of activated halogens with alkoxides include R, S,
Kittila, “Chemical Uses of Dimethylformamide,” Chapter 15, E. I. Chevon de Nemois & Cambany, Wilmington, Plowea 19898.

The base of the nitroimidazole (shown in Scheme 1) of Formula 1 and ζ, where R, , R, , R and Rs are as defined for Formula I, is an Adam platinum catalyst, hydrogen Treatment with and ethanol can be carried out at room temperature and atmospheric pressure. For further details,
M, H, Fischer, W
, H, Nicholson
and R8S, 7°Stuart, Ca
n, J, Chem, soc,, 39.501 (196
1), Other suitable processes using Raney nickel catalysts, Bennett, Jr., and H-T., Baker, J., Am., C.
hem, Soc, 2188 (1957). Stannous chloride can also be used. For more information, please refer to FieSer and FieSer.
(FieSer), +1 Reagents for Organic Synthesis”,
1, p. 1113, J. Willie, Sons, Inc., New York (1967) and references.

The imidazoles of 2000 [wherein R4 is H or CH, and R5 is H or C1-C4 alkyl] can be prepared by reacting the corresponding imidazole 40R6 H using processes known in imidazole chemistry. For example, V, which is produced by converting Bhagwat (B
hagwat) and F, L, Pyman.
, J.Chem.Soc.

See 127.1832 (1925).

The conversion from 39 to sulfonamides in which R4 is H or CH3 and R5 is H or C1-C4 alkyl is carried out by steps similar to those described in Scheme 1.

±'' for producing sulfonamides E and soil 1.
The functionalization of is shown in Scheme 3.

This step, when carried out under typical conditions for nitrogen alkylation or acylation, produces a mixture of isomeric sulfonamides and ±] in which R6 and R9 are defined with respect to Formula 1. do.

Takefu A [Formula 1, R4 is H or CH, R23 is C□-C3 alkyl or allyl, and [F] is a suitable protecting group such as, for example, a glycosyl group such as t-butyl. The compounds are prepared from the corresponding amino compounds by diazotization and subsequent coupling with S02 and MCI in the presence of a copper catalyst. The sulfonyl chlorides produced are converted to sulfonamides by treatment with ammonia solution. This process is shown in Process Formula 4.

The diazidation to produce the protected amino esters ±1 and subsequent diazonium chloride series is T,
Brown, G.

Shaw and G. Durant.
), J,Chem,Soc,,Perkin Tra
ns, 1.2304 (1980).

The reaction of diazonium chlorides to produce sulfonamides is also shown in Schemes 1 and 2. For the necessary details for these conversions, please refer to the literature cited above.

Intermediates of formula (c) where Q is Q-4, Q-5 or Q-6 can be prepared by a process similar to that described above for imidazole intermediates. Numerous publications are available which teach the chemical conversion and preparation of the pyrazole intermediates required for the present invention, for example, A. N. Kost and I-1. Groundberg. ), Adyan, Het.
erocyclic Chem 6゜347～42
9 (196B).

T.L. Jacobs, “Heterocyclic Compounds” (R.C., Elderfield, ed.), 5 vols.
Pages 45-161, Wiley, New York, 1957° A number of compounds of formula (C) where Q is Q-4 or Q-5, such as Danyu, can be used in the steps described in Scheme 13 and Scheme 5. It can be manufactured by

Reaction Scheme 13 The step of Reaction Scheme 13 is carried out using substituents that can remain after pyrazole metalation, such as R12 being H or CHZ, and RIG being C, -C4 alkyl, C6-C4 alkenyl, C3-C4 alkynyl or 5o2NR2゜R21
For something that is.

Are suitable.

The metalation reaction of pyrazoles is described by HoW, Gschwend and H, R, Rodriguez, "Organic Reactions", Vol. 26, 2.
3.24, Joan Wiley & Thump Incorporated, New York, 1979.

For the pyrazoles listed above and pyrazoles having groups sensitive to metalation conditions, the step of Scheme 5 can be used. For example, if R1° and R12 are of formula 1
as defined in , and R□□ is H,C
1-C3 alkyl, F, C1, Br, ORs s,
Compounds that are S (0) t NR2o R2l can be produced. Suitable protecting groups include and butyl.

R12 is H or CH3, and R11 is F, C
1, Br, oRl s, CO2R24゜S (0) mR
25 and 5o2NR20R21 and RIG is defined with respect to formula 1. Compounds of formula 605 and 1 are also disclosed for imidazoles in schemes 1 to 4 from intermediates of formula 605 and It can be manufactured using the process described above.

Q is Q-6, and R13 and R14 are H, C
, ~C, C4 Al R1,,F.

Compounds of formula (C) where C1,Br, C02R24,S (0) mR25 and S02 NR2o R2t, and R15 is H or CH3, can be synthesized using a suitable pyrazole intermediate as shown in Scheme 6. Produced by metalation at product 64.

Process formula 6: 1=1 Chlorosulfonation of pyrazoles and sulfonamides in which R11 is H, F, CI, Br or oRl, and Rl is C1-C3 atom. The conversion is carried out by the process taught in US Pat. No. 3,665, <)09.

Protection of the pyrazole ring can be carried out using the tetrahydropyranyl group CH20CH2CH2QCH3 (MEM). For details on this process using (TPE), see H.W. Gschwend and H.R. Rodriguez.
"Organic Reactions", 26.24 Sada, Joan Wiley and Sons φ Inc., New York, 1
For details on this process using (MEM), see E. J., Corey, J., 979;
L, Gourmet and P, Ulrich (
Ulrich), Tet, Let, 809 (1976
)checking.

Litation of protected pyrazoles and subsequent reaction with electrophiles can be performed using H,W.

Gschwend and HlR,
Rodriguez, “Organic Reactions”, 2
Volume 6, page 24, Joan Willey and Samp.
Incorporated, New York, 1979.

The subsequent reactions of steps 1 to 1 to produce suitable sulfonamide intermediates of the present invention are shown in Reaction Schemes 14 to 16.

Deprotection of sulfonamides and pyrazoles is carried out using acids such as trifluoroacetic acid. Using HCI in alcohol R240H resulted in esterification and deprotection simultaneously.

Sulfonamides are produced. The essence of this technology JJ
Alkylation with CH3I under conditions known to those skilled in the art produces other intermediates.

Furkylthio, alkylsulfinyl and argylsulphinyl groups are prepared from step 1 using the steps of formula 15 or 15a. Details of this type of conversion are described in US patent application Ser. No. 345.935, filed February 8, 1982.

1f 74 1I 74 II CH halo2 derivatives 2 and 1 can be obtained by deprotection as shown in Reaction Scheme 16.

Treatment of heteroaryllithium reagents with H79 halogens is known in the art. For details, see H and W.

Gushwend and H-R, Rodriguet, “Organic Reactions”, 26! ! ! , Joan Willey & Sons, Inc., New York, 1979. Using a similar process, R14 becomes C1
~C3 alkyl (dan1) and S 02 N R20R
Similar compounds are prepared which are 2□ (Tanhiki).

Formula (where Q is Q-7, Q-8, Q-9 or Q-10)
The sulfonamides of C) can be prepared by amination of the corresponding sulfonyl chlorides of 283 by methods known in the art. Sulfonyl chlorides, which are intermediate products of No. 83, can be produced by one of the methods shown in Reaction Scheme 17.

Scheme 17 % Formula % In Schemes 17A and 17B, a solution or suspension of the benzyl sulfide of 284 or the thiol of 285 in an aqueous acidic acid is reacted with at least 3 molar equivalent of chlorine at a temperature of about 0 to 15°C. Process with. The sulfonyl chloride of 283 can be isolated by diluting the reaction mixture with water followed by filtration or extraction with an organic solvent such as ether, methylene chloride or l-chlorobutane.

In reaction formula 17c, the bromide of Ni86 is about -78 to -20
It is treated with 1 mol of the same n-butyllithium in a solvent such as ether, tetrahydrofuran or dimethoxyethane at a temperature of 0.degree. The intermediate lithioheterocycle is added to excess sulfonyl chloride in a solvent such as hexane or ether at a temperature of about -20 to 0°C. Water is added to the reaction mixture, the organic solution is separated, and The sulfonyl chloride of formula 83 can be isolated by evaporating the solvent.

In Scheme 17D, the heterocycle of 287 is reacted at a temperature from about room temperature to the boiling point of chlorosulfonic acid over a period of 5.6 hours to 5.6 days.

The sulfonyl chloride of 283 can be isolated by treating the reaction mixture with excess chlorosulfonic acid, pouring it into ice water, and filtering the product or extracting it in an organic solvent.

In Scheme 17E, the heterocyclic amine of 288 is diazotized with sodium nitrite in a mixture of wood, concentrated hydrochloric acid, and acetic acid at a temperature of about -5 to 10°C. The resulting diazonium salt is added to a mixture of sulfur dioxide, cuprous or cupric chloride, concentrated hydrochloric acid and acetic acid, and the reaction mixture is stirred at a temperature of about 0°C to room temperature. The reaction mixture is diluted with water and filtered. The sulfonyl chloride of 283 can be isolated by extraction with an organic solvent.

Agriculturally suitable salts of compounds of formula (1) are also useful herbicides, and they can be prepared by a number of methods known in the art. It can be produced by treatment with a basic 7-ion alkali or alkaline earth metal salt (eg hydroxide, alkoxide, carbonate or hydride).

Similar techniques can be used to prepare quaternary amine salts.

Salts of compounds of formula (I) can also be prepared by exchanging one cation for another. Cation exchange can be carried out by directly treating an aqueous solution of a salt (e.g. an alkali metal or quaternary amine salt) of a compound of formula (5) with a solution containing the cation to be exchanged. It is most effective when the desired salt containing the exchanged cation is insoluble in water, such as a copper salt, and can be separated by filtration.

Exchange can also be carried out by passing an aqueous solution of a salt (e.g. an alkali metal or quaternary amine salt) of a compound of formula (I3) through a column filled with a cation exchange resin containing the cation to be exchanged. In this method, the cations of the resin are exchanged with those of the appropriate salt, and the desired product is eluted from the column.
It is particularly useful when the desired salt is water soluble, such as potassium, sodium or calcium salts.

Acid addition salts useful in the present invention are obtained by reacting a compound of Formula 1 or H with a suitable acid, such as P-toluenesulfonic acid, trichloroacetic acid, and the like.

The preparation of the compounds of the invention is briefly illustrated by the following individual examples. Unless otherwise specified, temperatures are in degrees Celsius.

52.2 g of ethyl inthiocyanate were added dropwise to 79.8 g of aminoacetaldehyde diethyl acetal in 600 ml of ethanol. After the addition was complete, the mixture was heated to reflux for 30 minutes. Ethanol was removed under reduced pressure on a rotary evaporator. 10% MCI of 1 liter
was added, the mixture was washed for 30 minutes, and then cooled to room temperature. The pH of the solution was adjusted to 3 with 50% NaOH. The product was extracted with CH2C12. The extract was then dried using Mg5O, 11! and concentrated to 1M on a rotary evaporator. The crude product was chromatographed on silica gel using 75% ethyl acetate-hexanes. 18.4 g of the title compound were obtained in the form of a solid with a melting point of 71-72°C.

17.0 g of 1-ethyl-IH-imidazole-2- in 180 ml of 2NHCI cooled to 0 to -8°C
The reaction temperature was kept below 10° C. during the addition. After the addition is complete, the reaction is FI for about 30 minutes at 0-10°C.
J′l was stirred. While maintaining this temperature, PI (4.
Sufficient 50% NaOH was added to the reaction to raise the temperature to 0. The white precipitate formed was filtered, and 0-
It was added to a room ml of concentrated aqueous ammonia solution that had been cooled to 10°C. The mixture was stirred for 30 minutes and then concentrated on a rotary evaporator. The concentrate was boiled three times with cH3CN and the insoluble material was filtered and discarded.

The CH3CN extract was dried over MgS Oa, filtered, and S-condensed on a rotating base. 11.8 g of the title compound were obtained in the form of a solid with a melting point of 123-125°C.

Q=Q-1, Rt=C2Hs, R2=R3=)(:A
=A-1, z=cH, x=ocu3, Y=CH3;
R = H) c7) 1.75 gcy) in 80 ml dry CH2Cl□
1-Ethyl-IH-imidazole-2-sulfonamide was added to 6,0 ml of (CH3) under N2 at room temperature.
s A 1 (7) to 4-? 2. Treated dropwise with OM solution. The mixture was stirred for 15-30 minutes.

Then 1.97 g of methyl (4-methylpyrimidin-2-yl)carbamate was added and the mixture was refluxed for 16 hours. Enough 5% aqueous acetic acid was then added to lower the pH to 3.0. The crude reaction mixture was
Extracted three times with H2Cl2. The extract was M g S 0
4, filtered and concentrated on a rotary evaporator. The 1:i mixture was boiled with hot ethyl acetate and the product was filtered to give 0.8 g of the title compound as a white solid with a melting point of 178-179°C (d).

45g in 120ml of water and 120ml of 12N hydrochloric acid
of 1-methylpyrazol-3-amine was added at -10 DEG C. followed by dropwise addition of 33.9 g of sodium nitrite dissolved in 75 ml of water. The temperature was kept at -10°C, and after the addition was complete the mixture was heated for an additional 30°C.
Stir for a minute.

The solution in part L was then heated at -lO°C with stirring for 3
48ml (7) acetic acid, 5.8g CuCl and 48ml
The mixture was added in portions to a mixture containing 1 (liquefied) dimorphic sulfur. After stirring for 1 hour at −10° C., the reaction mixture was warmed to 10° C. and poured into 1500 ml of water and water.

The resulting mixture was extracted with three 500 ml portions of methylene chloride. Combine the extracts and add anhydrous magnesium sulfate to
Dry over F, filter and evaporate in vacuo to yield a red oil. This material can be purified without further purification.
-Methyl-pyrazole-3-sulfonamide.

1-Methylpyrazole-3-sulfonamide chloroform (100ml), 13.6gc7) A mixture containing 1-methylpyrazole-3-sulfonyl chloride and 13.6g of ammonium carbonate was heated under reflux for 6 hours. , cooled, filtered, and washed the solid with water. 50
% ethanol-water, the water-insoluble solid melts at 149-151'c and 3100 and 3200 cm-', corresponding to NH, in the desired product.
showed an infrared absorption peak of

Analysis value calculated for C4H7N 902 S: C,2
9,8;H,4,38;N,26.07. S, 19.9 Actual value: C, 29,3; H, 4,6; N, 25.3. S, 19.2 20 ml of chlorosulfonic acid were added dropwise to 6.0 g of lH-imidazole-5-bromo-1-methyl at room temperature with stirring. The reaction mixture was heated to 100°C for 16 hours, then to 140°C for 4 hours. The reaction mixture was cooled to 0° C. and poured onto crushed ice, the tan solid formed was collected by filtration and dried under vacuum. This crude sulfonyl chloride (melting point 84-86°C) was
1 of anhydrous ammonia and left overnight at room temperature. Remove excess ammonia under a stream of nitrogen.

The resulting solid was then recrystallized from 25 ml of water.
3.2 g of desired sulfonamide, melting point 204-20
5.5°C.

59 g (0,615 mmol) of 1,3-dimethylpyrazole was added slowly to 300 g (2,5 mmol) of chlorosulfonic acid at 0°C. 6 The reaction was warmed to 90°C for 3 hours, cooled and Pour over 500g of ice,
The aqueous solution was extracted with 3×100 ml of ether. The organic extracts were dried over anhydrous sodium sulfate and filtered. The ether solution was added dropwise to a solution of 55 g of anhydrous ammonia (2.5 mmol) in 250 ml of ether.

- After setting up overnight, water was added and the phases were separated. The aqueous solution was extracted with ethyl acetate, the organic solutions were combined and dried over anhydrous sodium sulfate. After removal of the drying agent, the solvent was removed in vacuo to give 20.5 g of product, mp 97-105°C.

Q=Q-6, R, 3=R□5 =CH3, R14=H,
A=A-1, Z=CH, X=OCH3, Y=CH,, R
=H) 1,3-dimethylpyrazole-4-sulfonamide (1
, 75 g, 10 mmol) in 100 ml (7) 1.2-
';''70 added to loethane. Toluene (2M, lo
ml) of trimethylaluminum was added. The reaction was brought to reflux, stirred and 4-methoxy-6-methyl-2-aminopyrimidinecarbamono-dimethyl (2.0 g, 10 mmol) was added. - After refluxing overnight, the reaction was cooled, poured into ice water and treated with 60 ml of 10% HCI. The phases were separated, the organic phase was extracted with methylene chloride, and the organic solutions were combined. The organic solution was dried with anhydrous sodium sulfate and decolorized with charcoal. The solvent was removed in vacuo. The solid was triturated with ether and collected to 1.5 g, mp 207-210'C.

A. Benzyl mercaptan (24.8 g) in lO, 8 g
of sodium methoxide in 100 ml of ethanol. After stirring for 15 minutes, the ethanol solution of sodium benzyl mercaptide was mixed with 30.8 g of 2,4-diglolothian'-ol [P, L/Reynaud et al., Bul 1. Soc, Chim
, France, 1735 (1962)], the temperature is between 28 and 4
When the exotherm, which rose to 8°C +h/h, had ceased, the suspension was refluxed for 1 hour and then the solvent was evaporated. Cold water (300
ml) to the oily residue and the aqueous mixture f 11!
Extracted with methylene chloride. The organic solution was washed with water, then with saturated brine, then dried over magnesium sulfate E, filtered, and the solvent was evaporated to give 43.8 g of 4-
Chloro-2-phenylmethyl-thiothiazole was given as a brown oil.

B, a mixture of 43.8 g 4-chloro-2-phenylthio-thiazole, 225 ml acetic acid and 25 ml water was cooled to 4°C and 2
9ml of liquid chlorine was added dropwise. When the chlorine addition was complete, the pale yellow solution was stirred at 0° C. for 15 minutes and then poured into a 1200 ml 7R tube. Extract the essential mixture with ether2. The organic solution was washed with water, then dried over magnesium sulfate, filtered, and the solvent was evaporated.

The remaining yellow oil is dissolved in 200 ml of tetrahydrofuran and 50 ml of ammonium hydroxide is dissolved in 25-3
Added dropwise at 0°C. The brown anti-yield mixture was stirred at room temperature for 1 hour. The reaction mixture was evaporated, diluted with 200 ml of water and acidified with acetic acid. The aqueous mixture was extracted with methylene chloride, the 641 solution was washed with water, dried over magnesium sulfate beads, filtered, and the solvent was evaporated.

The resulting oily solid was triturated with 300ml of hexane, filtered and washed with hexane to give 7.7g of the title compound. Melting point: 137-141.5°C.

NMR (CDCI3/DMSO-do): δ7.5
(s, IH, 5-CH) and 7.7 (broad S, 2
H, S02 NH2), IR: 3.06 and 3.28
For (SO□NH2) - Jitsudera 111A R2s = C1, R36 = H, Z = CH, X = Y =
OCH3) To a solution of 1.6 g of 4-chloro-2-thiazolesulfonamide in loOml of methylene chloride/fI was slowly added by syringe 4.4 ml of a 2.0 M solution of trimethylaluminum in toluene under a nitrogen atmosphere. The reaction mixture was stirred for 10 minutes and 1.9 g of N-(4,6-
Add methyl cymethoxypyrimidin-2-yl)carbamate.

The reaction mixture was then refluxed for 18 hours. The reaction mixture was cooled to O''C and 55 ml of 5% hydrochloric acid was added dropwise to give a flocculent solid. The reaction mixture was extracted with 100 ml of ethyl acetate. The organic solution was washed with brine, dried over magnesium sulfate, filtered, and the solvent was evaporated.
Slurried, collected, washed with hexane, and dried to give 1.25 g of the title compound as a white solid.

Melting temperature: 182-183°C (d), IR: 2.98 g, 3.25 g (NH), 5.80 g (C=0).

NMR (CDCIi/DMSO-da): δ3.9
0 (5,6H,0CH3), 5.9(s,l)I,
pyrimidi7CH), 7.95 (s, IH, isothiazole CH) and 11.2 (S, LH, NH).

Analysis value calculated for C10H1oCI N50 s S 2: C, 31,62; H, 2,66; N, 18.4
3 Actual value: C, 31,8; H, 2,7; N, 18.5 C, 31,8; H, 2,7; N, 18.4 X1I (1'' A, benzyl mercaptan (24,8 g ), 10.8
of sodium methoxide in 100 ml of ethanol was added slowly. After 10 minutes, the reaction mixture was
Heat to 5° C. and add 23.8 g of 4-chloro-thiazole [P, Reynaud et al., Bull
, Soc.

Chim, France, 1735 (1962)] in ethanol was added dropwise. When the addition was complete, the reaction mixture was
Refluxed for an hour. The reaction mixture was cooled and most of the solvent was based. Add cold water (300 ml) to the residue;
and the aqueous mixture was mixed with 200 ml of ether and then 2
Extracted with 00ml methylene chloride. - Wash the combined organic solutions with brine and dry over magnesium sulfate.

The tumor was removed and the solvent was evaporated. The resulting yellow oil was distilled to yield 15.6 g of 4-(phenylmethylthio)thiazole, boiling point 122-134°C (0.6 mm).

B. A mixture of 15.6 g of 4-(phenylmethylthio)-thousandazole in 75 ml of acetic acid and 25 m of water was cooled to -5°C and 12°0 ml of liquid chlorine was added dropwise at -5°C. did. Addition complete 1. When cooled, the yellow solution was stirred at 0° C. for 20 minutes, then poured into 500 ml of ice water and the aqueous mixture was extracted with methylene chloride. The organic solution was washed twice with water, dried over magnesium sulfate, filtered, and the solvent was evaporated to give a yellow oil that partially crystallized on cooling. The crude sulfonyl chloride was dissolved in lOml of tetrahydrofuran and 12,0ml of ammonium hydroxide was added at 5-10°C.
was added dropwise. The resulting brown suspension was allowed to warm to room temperature and then concentrated to an oily solid. Addition of 200 ml of wood and 100 ml of methylene chloride to the oily solid resulted in a solid at the interface. The solid was collected, washed with water and then hexane, and dried to give 3.8 g of the title compound as a brown solid.

Melting point: 142-146.5°C, IR: 3. l and 3,
2p (502NH2).

NMR (CDC13/DMSOdo): δ7.15
(wide s, 2) 1, S02 NH2), 8.1 (
d, LH,OH) and 8.6 (d, LHlCH).

R2a=R27=H, Z=CH, X=OCH3, Y=
CH,) By using the method described in Example 10,
3, 0.98 g of 4-thiazolsulfonamide was dissolved in 1.3 g of N-(4-methoxy-6
-Methylpyrimidin-2-yl) methyl carbamate yielded 0.7 g of the title compound in the form of an off-white color.

Melting point 196-200'C(d), IR: 5.89l(C
= O).

NMR (CDCl,/DMSO-d,): 62.48
(S, 3H, CH3), 3.90 (s, 3H, 0C
R3), 6.45 (s, IH.

Pyrimidine CH), 8.67 (d, LH, Thiasole CH), 9.26 (d, LH, Thiasole CH), 1
0.5 (s, IH, NH) and 13.2 (s,
IH, NH).

11.1 g of honamide 4-bromo-5-ethoxy-2-methylthiazole [D,S, Tarbell
et al., J., Amer, Chem, S.;

C0, 72, 3138 (1950) Method Niyori V1
A solution of 50 ml of ether in ether was cooled to -60°C and heated for 3 hours, keeping the temperature below -45°C.
5.9ml n-butyllithium 1.7M in hexane
The solution was added dropwise. The resulting dark-brown suspension was further diluted with 25 ml of ether and diluted from −50 to
Stirred for 20 minutes at a temperature of -30°C. Temperature -30~-
The ether suspension of lithiothiazole was added to 8.0 ml of sulfonyl chloride via a syringe, keeping the temperature at 20°C.
Added to 0 ml of solution in hexane. After the suspension was stirred at -30 °C for 15 min, it was warmed to -5 °C and the stirred reaction mixture for 3.5 h was poured into 500 ml of ice water, the biphasic suspension was diluted with ether. Extracted twice. - The combined organic solution was washed with water and brine, then dried over magnesium sulfate E, filtered and the solvent was evaporated. The resulting oily solid was dissolved in 150 ml of tetrahydrophthane, the solution was cooled to 0°C, and 6.7 ml of
1 of ammonium hydroxide was added dropwise. The brown suspension was allowed to warm to room temperature and stirred for 3 hours. The solvent was evaporated and the remaining black oil was partitioned between methylene chloride and water. The organic phase was washed with water and then brine, then stirred with magnesium sulfate and charcoal. The mixture was filtered through Celite and the solvent was evaporated. The resulting brown oily solid was triturated with 1-chlorobutane to give 4.2 g of the title compound as a tan solid.

Melting point 118-120°C, IR: 3.05 and 3.15
(SO□NH2).

NMR (CDC13/DMSOdo): δl, 25
(t, 3H, CH3), 2.60 (S, 3H,
CH3), 4.22 (q.

2H,0CH2) and 6-1o (wide s, 2H, S
02 NH2) - midin-2-yl aminocarbonyl -2-methyl-
4-thiazolesulfonamide (I:Q, =Q-7, R
2s=CHa.

R27=OC2Hs, Z=CH1 X=Y=OCH3) By using the method described in Example 1O,
3.3 ml of trimethylaluminum in toluene 1.
1.33 g of 5-ethoxy-2-methyl-4-thiazoolsulfonamide was dissolved in 1.4 g of N
Reaction with methyl -(4,6-cymethoxypyrimidin-2-yl)carbamate gave 1.2 g of the title compound.

Melting point 140-143°C.

IR: 1710 cm-' (C=O).

NMR (CDCI3): δ1.5 (t, 3H.

CH3), 2.6 (S, 3H, CH3), 3.95 (
S, 6H, 0CH3), 4.3 (q.

2H,0CH2), 5.8 (s, LH, pyrimidine CH,), 7.5 (wide s, LH, NH) and 13.
0 (S, 0.67H, NH).

280 ml of methyl bonate A, 31.3 g of potassium t-butoxide
The solution in tetrahydrofuran was cooled to -50°C and added dropwise at -50 to -40°C to a solution of 27.7 g of methyl isocyanoacetate in 230 ml of tetrahydrofuran. The resulting brown suspension was stirred for 15 minutes, then cooled to -78°C and added dropwise to a solution of 16.8 ml of carbon disulfide in 225 ml of tetrahydrofuran, keeping the temperature below -150°C. A pinkish-brown thick suspension was added over a period of 15-20 minutes.
Warmed to ℃. A solution of 33.3 ml of benzyl bromide in 140 ml of tetrahydrofuran was added to the reaction mixture at -1
It was added dropwise at 5--5°C.

The reaction mixture was stirred at room temperature for 30 min and refluxed for 20 min at 1
It was then cooled and most of the solvent was evaporated. 10100O ice water was added to the oily residue. The dark brown solid was collected, washed twice with water, then hexane, and dried to yield 68.8 g of 5-(phenylmethylthio)-
Methyl 4-thiazolecarboxylate, melting point 90-92°C,
gave.

B, 39.8 g of methyl 5-(phenylmethylthio)-4-thiazolecarboxylate in 225 ml of acetic acid and 2
The solution in 5 ml of water was cooled to 3°C and 23.9
ml of liquid chlorine was added dropwise below 10°C. The yellow-brown solution was stirred at 5-10 °C for 45 min, then 1200 m
1 of ice water to give a yellow oil that partially solidified on standing. The crude reaction product was collected, washed with water, then four times with hexane, and dried to give 29.4 g of methyl 5-(chlorosulfonyl)-4-thiazolecarboxylate, mp 94-97. 5°C. .

A solution of 28.9 g of methyl 5-(chlorosulfonyl)-4-thiazolecarboxylate in 150 ml of tetrahydrofuran was cooled to 0°C and 6.6 ml of liquid ammonia was added dropwise at 0-10°C. 24 The solution was allowed to warm to room temperature and stirred for 1 hour. 6 The reaction mixture was filtered, the ammonium chloride was washed with tetrahydrofuran,
The solvent was then evaporated from the filtrate. The remaining solids were slurried in hexane, collected, and dried to yield 25.0 g.
The title compound was obtained as a tan solid. Melting point 138
~140°C, IR: 3. For OL and 3.1 (S02
NH2) as well as for 5.8 (C=O).

NMR (CDC13/DMSO-da): δ4,
O(s, 3H, 0CR3), 7.2 (wide s, 2
H, S02 NH2) and 9.0 (s, IH, thiazole CH).

A mixture of 11.1 g of 5-(aminosulfonyl)-4-thiazolecarboxylate, 5.6 ml of butyl isocyanate and 0.17 g of diaza[2,2,2]bicyclooctane in 150 ml of xylene was heated to reflux. While keeping the temperature above 130℃, phosgene (
4.2 ml) was added in large portions to the reaction mixture. When the last 0.5 ml of phosgene was added, the reaction temperature was 12
The reaction mixture, which had cooled to 4°C, was refluxed for 1 hour, then the dry ice condenser was replaced with a water condenser, and the mixture was refluxed for 30 minutes under a slow stream of nitrogen. The reaction mixture was cooled, filtered twice under nitrogen, and the solvent was evaporated from the filtrate to give the title sulfonylisocyanate as a thick yellow oil. IR: For 4.45 (S02NG
O).

The crude sulfonyl isocyanate was dissolved in 50 ml of methylene chloride for reaction with the 7-minoheterocycle.

χ Seal” 1 5- 4.6-Simethoxypyrimidine-2-Q=Q
-7, R27:C02CH3・R268H, Z=CH
,
2,2,2] To a suspension of bicyclooctane crystals in 5 ml of methylene chloride was added 11 ml of the methylene chloride solution prepared in Example 16. After the addition, a clear solution appeared and a precipitate began to form after about 30 minutes. The suspension was stirred at room temperature overnight. The solid was collected, washed with -chlorobutane, and dried to give 1.2 g of the title compound.

Melting point 172-174°C (d).

IR: 1721 and 1710 cm-' (2XC=0
).

NMR (CDC13/DMSO-d,): δ3.97
(s, 3H, 0CR3), 4.02 (s, 6H, 0C
H3), 5.8 (s, IH, pyrimidi 7CH), 9.1
(s, IH, thiazole CH), 10.0 (wide s,
LH, NH) and 13.1 (wide s, IH, NH).

A, 5.05 g of 50% sodium hydride in mineral oil was washed with hexane and suspended in loOm+ dimethylformamide. Addition dropwise to this suspension of a solution of 19.57 g of ethyl 4-hydroxy-2-methyl-5-thiazolecarboxylate in room ml of dimethylformamide reduced the reaction mixture to 7.5 g, which produced a thick yellow gel.
Diluted with 5ml dimethylformamide and stirred for 30 minutes. A solution of 14-23 g of dimethylthiocarbamyl chloride in 50 ml of dimethylformamide was added dropwise to the thick slurry and the reaction mixture was then brought to 85-95 ml of dimethylformamide.
℃ for 45 minutes. The resulting brown suspension was cooled and poured into a dilute solution of 5.7 g of sodium hydroxide in 1200 ml of water. The aqueous mixture was extracted once with benzene and twice with ether. - The combined organic extracts were washed twice with water, then with brine, then dried over magnesium sulfate, filtered, and the solvent was evaporated with N to give an oil, which was partially crystallized into. The crude reaction product was slurried in hexane, collected, and dried to yield 13.1 g of ethyl 4-[(dimethylamino)thioxomethyloxy]-2-methyl-5-thiazolecarboxylate, mp 87. ~90°C.

B. A 12.3 g sample of the compound of Part A was heated to 170-195° C. for 1.5 hours under a nitrogen atmosphere. The dark reaction mixture was cooled and dissolved in methylene chloride. Evaporation of the solvent gave a black oil which crystallized upon stirring. Recrystallization from hexane-ethyl acetate gave 9.2 g of ethyl 4-[(dimethylamino)carbonylthio]-2-methyl-5-thiazolecarboxylate, mp 84.5-85.5°C. Ta.

C, 21.5 g of a sample of the compound prepared in Part B was added to 2.
A solution of 7 g of sodium in 200 ml of ethanol was added and the reaction mixture was stirred at room temperature overnight. The dark brown suspension was concentrated, the residue was dissolved in 500 ml of water, and the aqueous solution was acidified with cold dilute hydrochloric acid. The aqueous mixture was extracted with methylene chloride, the organic solution was dried over magnesium sulphate, filtered and the solvent was evaporated. Cold water (200 ml) was added to the oily solid and the resulting solid was collected, washed with water and dried to give 4-mercapto-
This gave ethyl 2-methyl-5-thiazolecarboxylate, melting point 62-66°C.

D, 14.4 g of a sample of the compound prepared in part B, 8
A solution in a mixture of 0 ml acetic acid and 20 ml water
℃ and add 11.3 ml of liquid chlorine from 0 to 8℃.
was added dropwise. The fA brown M solution was stirred at about 5° C. for 30 minutes and then poured into 500 ml of water. The aqueous mixture was extracted twice with ether, the organic solution was washed twice with water, dried over magnesium sulfate L, filtered and the solvent was evaporated to give an oil. 1 00ml of crude sulfokol chloride
of tetrahydrofuran and the solution was heated to 5°
Cooled to C. Ammonium hydroxide (10.4ml)
was added dropwise and one reaction mixture had a pH <7. Further ammonium hydroxide (4.4ml) was added, the reaction mixture was warmed to room temperature and stirred for 2 hours. The solvent was evaporated and 300ml of cold water was added to the remaining oily solid. The resulting solid was collected, washed with water, and dried to give 8.1 g of the title sulfonamide, mp 129-131.5°C.

IR: 3380 and 3225 cm-'(SOzNH2
) and 1705 cm-' (C=O).

18±'' 5-ethoxycarbonyl-2-methyl-4-thia85m
7.5 g of the Ma sulfonamide of Example 17, 3.4 ml of butyl incyanate, in 1 of xylene.
and 2. A mixture of 3 diaza[2:2,2]bicyclooctane crystals is heated to 136°C, and 2.
3 ml of phosgene was added dropwise. When the phosgene addition was complete, the reaction temperature had fallen to 126°C. The reaction mixture was refluxed for 30 minutes, the dry ice condenser was replaced with a water condenser, and the mixture was refluxed for an additional 30 minutes under a slow stream of nitrogen.The reaction mixture was cooled and filtered under nitrogen. Evaporation of the solvent gave the title sulfonylisocyanate as a tan oil.

IR: 2240 cm-' (S02 NGO) and 1
760cm” (C=O).

The crude isocyanate was dissolved in 25 ml of methylene for reaction with the heterocyclic amine.

IjltA tongue carpone ethyl (I; Q=Q-8゜R2a =C
H3, R2s = CO2C2Hs, Z=N, X=OCH
3, Y=CH3) A 7 ml portion of the methylene chloride solution of the sulfonylisocyanate prepared in Example 18 was added to 0.35 g of 4-methoxy-6-methyl-1,3,5-triazin-2-amine and one Diaza[2,2,2] was added to a stirred suspension of bicyclooctane crystals in methylene chloride. The reaction mixture was stirred overnight. 'Tf! The bright solution was concentrated to a tan oil. Long abrasive with ether gives a solid which is collected, washed with ether and dried to 0.
This gave 48 g of the title compound, melting point 126-130°C.

I R: I 725o, j: and 1720cm-' (2
XC=0).

NMR (CDC13): δ1.35(t, 3H, CH
I), 2.6 (s, 3H, CH3), 2.75
(S, 3H, CH3), 4.4 (q.

2H,0CH2), 8.2 (wide s, IH, NH) and 12.6 (wide s, IH, NH).

20 g of 3-chloroisothiazole and l.

A mixture of Oml chlorosulfonic acid was allowed to flow for 0.5 hours, cooled and heated to 90 °C overnight, then 2 days J
ut Amount R was made. The aqueous mixture was extracted with ether, the organic solution was washed with water and brine, then dried over magnesium sulfate, il! filtered and the solvent was evaporated. The residual oil was dissolved in ether and treated with gaseous ammonia for 1 hour at 10°C. The reaction mixture was filtered and the filtrate was evaporated. The residual solid was washed with hexane, collected, and dried to give 8.2 g of the title sulfonamide.

Melting point 110-116°C.

IR: 3400 and 3270 cm-'(SO□NH2
).

Sulfonamide prepared in Example 21 with 4.0 g of cyanate, 8
．． 0 ml butyl isocyanate, o.

A mixture of 1 g of diaza[2,2,2]bicyclooctane and 40 ml of xylene was heated to reflux, and 2.
The reaction mixture was successively treated with a solution of 4 ml of phosgene in 10 ml of xylene, refluxed for 4 hours, then cooled.
Then the solvent was evaporated. The residual crude sulfonyl isocyanate (IR-2250 cm-') was dissolved in 50 mH7) methylene chloride.

3-Chloro-N-46-dimethylpyrimidin-2-yl aminocarbonyl-4-inchazolesulfonamide (1,Q=Q-10,R3,=C1,Z=CH,X
=Y=OCH3) 3-chloro- produced in Example 22
One portion of a solution of 4-inchazolesulfonylinocyanate in methylene chloride was added to 0.2 g of 4,6-dimethyl-2-pyrimidineamine and the mixture was stirred at room temperature for 0.5 hour. The solvent was evaporated and the remaining solids were abraded with ether, collected and dried to 0.5%.
This gave 5g of the title compound. Melting point: 136-140°C.

IR: 1720 and 1700 cm' (C=O).

NMR (CDC13): 2.5 (s), 6H.

CHa), 6.8 (s, l) (, pyrimidine CH) and 9.5 (s, IH, isothiazole CH) A, 52
．． 0 g of 4-amino-3-inthianylcarboxylic acid hydrochloride [K, Gewald and P,
Bil Iman, Liebi
s Ann, 1542 (1979)] in 300 ml of methanol was cooled in a water bath and 10 ml c) 1! Thionyl chloride was added dropwise. The reaction mixture was refluxed for 3 hours, cooled and the solvent was evaporated. Collect residual solids, wash with ether,
and dried to form 47.5 g of methyl 4-amino-3-isothiazolecarboxylate hydrochloride, melting point 170°C (d
), I made a potato.

B, 100 m of amine hydrochloride prepared in part A of 38 g
A suspension of 1 in acetic acid was cooled to 15°C and rooml
diluted with concentrated hydrochloric acid. The mixture was cooled to OoC and a solution of 16 g of sodium nitrite in 40 ml of water was added dropwise for 30 minutes. 1. The reaction mixture was stirred at -5 to 0.degree. C. and then 5 g of cuprous chloride, Added in portions at 0° C. to a stirred mixture of 5 ml (7) concentrated hydrochloric acid, 40 ml of i-yellow dioxide and 200 ml of acetic acid.

After 1 hour at about 5°C, when gas evolution had stopped, the reaction mixture was poured into 400 ml of ice water and 3
It was left for 0 minutes. The resulting solid was collected and dried over 25.0 g of methyl 4-(chlorosulfonyl)-3-isothiazolecarboxylate, mp 42-46°C.

C, 21.4 g of sulfonyl chloride prepared in part B
00 ml of solution in tetrahydrofuran was cooled to -70 °C and treated with 5.5 ml of liquid ammonia. The reaction mixture was warmed to -20 to -10 °C, stirred for 15 min, and adjusted to pH 7 with concentrated hydrochloric acid. did. The resulting solid was collected, washed with tetrahydrofuran, and dried.
This gave 18.8 g of the title sulfonamide.

Melting point: 107-113°C.

NMR(CDCl3/DMSOds)
: δ4, O(s, 3H,0CH3), 7.0
(wide s, 2H, 302NH2) and 9.3(s, 1
H9 isothiazole CH.

9.0 g of the sulfonamide prepared in Example 24, 6
ml butyl isocyanate, 0.2 g diaza[2,
2,2] A mixture of bicyclooctane and 150 ml of xylene was heated to 125° C. and a solution of 4 ml of phosgene in 6 ml of xylene was added dropwise. A small amount of tar formed upon completion of the addition. A 0.2 g portion of diaza[2°2.2]bicyclooctane was added and the mixture was refluxed for 2 hours. The reaction mixture was cooled, decanted from the tar, and the solvent was evaporated to give the sulfonylisocyanate an orange color. It was given in oil form. Crude sulfonyl isocyanate was prepared for reaction with heterocyclic amines.
ml of methylene chloride.

IR: Published by 2240cm (So, NGO) and 1735
cm 1 (c=o).

Q=Q-10, R3, =CO2CH3, Z=CH, X
= Y = C)Is) To a solution of 0.5 g of 4,6-dimethyl-2-pyrimidineamine in 10 ml of methylene chloride was added 10 ml of Example 2.
A solution of the sulfonylisocyanate prepared in step 4 in methylene chloride was added and the reaction mixture was stirred for 15 minutes. The solvent was allowed to evaporate and the residue was abraded with methylene chloride and ether. Collect the solids and dry-blast them to produce 1
．． This gave 0 g of the title compound.

Melting point 167°C (d), IR: 1735.1720 and 1700 cm (C=O).

NMR (CDCI3/DMSOda): δ2.4 (
5,6H,CH3), 3-9 (s.

3H,0CH3), 6.9(s, LH, pyrimidi7CH
), 9.8 Cs, IH, isothiazole CH) and 11.8 (broad s, IH, NH).

Compounds 1 to X were manufactured by the methods described in Examples 1 to 26 or modified methods thereof.

N1 Otsu δδδ2δ OtsuCtl Work I Work Work = I Work t1 Eee I Work I Work rl Work I Eee I Work δ2□2δδδδδ2□2□2□δδδE E E E E E E E E E E E E E E I
Work Work E E E E E E E E E E
E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E
I E E E E E E E E I I Engi
Shima Engineering: JuCI Engineering Second Engineering: Engineering Engineering: , M , l'%, f , f, f, f, l"tif
fδ,,'%fi Otsu δ δ5 Otsu OtsuδOtsu δOtsu Roδ: E E E E E E E E
E E E E E = E E E E
E E E E E E E E: E
E I E E I E E E E
D, is 1'l A +'% pδ δ
δ δ r (j δ Otsu δ δ 工υ E E E E E
: E E E E E
E E Table Ia (Continued) RI R2R3 Work
5 ヱ ni Jλ し 2 SΣC 5-te 0 (
38HHCHO-1,O.

Table Ia (continued) R1-5dan A 5 ヱ 54- -””2”3　H) (HCHO-+30:H.

? Table ra (continued) R155 danl 5 engineering 2? -"2""C戎H3HHHC)'I CH3工H3-C
)I2-C-OCH2C)-13HHHCH0-130
CH3-CX, -C-OCH2C) (2CH3HHHC
HO-1,DCH3-C)I2-c-oc+(c+,)
2HHHCHc) (3o:+3-c7-B-o(c+2
)3cH3H1-I HCHO(3ccH3? 1%-C5)-1(C)R3)2HHHCHCl-1,
OCH3-O(, -C-O-0-1(CH3)C)+2
O-13HHHCHCH,QC)4゜-C-OCH3)
(HHC1-I CH30CH.

-C-QC! -t, CH, Hl(HC1-IC)L
, OCH3? -C-CCH20-12C)t3HHHCHCH,OC
H.

Table 1a (continued) '4 Fll R2R3RZ
X Y m, o, ('C)-C-QC)I(CH3
)2HHHCH0(3CCH.

-C-0(C1(,,), CI-L, HHH
O-I CH, QC) (.

-C:)I2-CH(C)43)2HHHCHC)t
3CCH.

″Y) 4 (to C) CFt,, CJ HHH 0
83 “83 一轡-C-OCH20(=cH28HH
CHO(,CC)(.

-C-OCH2CH=CH21-I HHCH0(3
CC)'I3-Ca-o(2-O'I=CH-()(3
1-I H) I CHCH3CC) (.

-O(, -C-OCH21jCHHHHC)IC)43
(X:')(.

-C-OCI-12C2CHHHHCHC1 (50CH
3-C-CCI-12-(,,C-0-1,l-I
H) 4 CHCH, Eng 1-1゜ Table Za (continued) R1 Ni ni ni 2 Dan l Wang ヱ
Nyoλmi2sΣ-C-OC) (2C1-12C1l
-I HHO-10-1300H3-c-oc) (2c
Z Engineering I HHHCH Kamo Engineering H3-C-5C) 43
HHH Ro (R30:H.

Me5-(CH2)3CH3HHHCHC)(, Engineering H3
-C-5-0(2-0-1=cH2HHHC)IC)
I3CCH.

〇10-5-Duck heart=CH-0-I3HHHCHu, 5-C
-N(CH3)2HHHCH0-130CI-1゜〇-C-N(CH3)fj(,,CH3HHHYarakamoko8゜-C-N(C)(2CH3)2HHHC)(CH3CC
H3 table Za (continued) '1 55dan26 E4. . ,,. . , Table Xa (
(Continued) R155 Dan Niku Eyu Genmyo Xa (Continued) RI R2R3RZX Y5! Table ra (Continued) -55 Dan L -5 Ward Table Ia (Continued) R1 Ni! 2 dan L animals ヱ
Nigo LQSΣ-0-120 (3HHHA-
2H -o(2CH3HHHA-3C1 -0-I2CH3HHl-I A-30:F2)(
-OL, CH3HHHA-4H -O-12C)'I3HHHA-4C1-0-12C1
-13HHHA4 0:F2HRI R2R3R
AX2 Y2
ffa”aT,f,s”5δδδδδδδδδδδδδ
δro= E E E E E I E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E Nl z
z z z z z z z z z z
z z z2□2δδδ2□2δδδ2□δδ
δδE E E E E E E E E E E E E E E I Engineering Engineering I4 to xl ff6 t! 3'5"5" cff (I3
” (I3” (!;” (!i ff cff ff
f et al. Otsu δ Otsu δ 5 δ δ δ δ δ δ δδ 2 Ha
Hateeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee 1 ni t5'5'5'gT fftfftfffftfr[
δδδδδδδδδδδ2□2 δδδδ2□δδ2E E E E E E E E E E E E E
E E E E E E x E E xl E E E E E E E E E E E E E E E E E E E E E E E E δδ roδ δ δ δ δ δ δδδz z z z z z z z z z ZE E E E E E E E E E E E E
E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E
E E E E E E E E E I E E E E E E E E E E E E E E E E E E E I --16+7
- 15 degrees 10 1, ;) (3CI HHN CC) (3CCH,
194-21R6R5"a Dan △ 4-Yu GenC) t3CH2HHHA-4LIU?2"'R6R5R
4RA
%,,'%,l'l i,f f,f ffδδ
δδδ ro6δδδδδδδδroe E E E E E E E E E E E E E E E E E E E E E E E E E E E I I Eng, rf i, rf,, FS,
,'% ii score 3"5"5"6"5"roffFl)"ro゛iiro"F,"FT:C" i r
'r:"100ii hole a'teTi100ii102□2.δ'
? 32δOtsu2OtsuOtsuδzzzδδδδ2□2E E E
E E I Work I I I E E E E E E E E E = Work 1 Work I E E E E I Work Work I Work Work = = E E = E
E E E E Eq q ”tf q 工I EEEEE M
Product M product Moromi mellow Rorororororo δδ2δδδδδδδδc!
liδroδδδδδδ2zE E E E E E E I E E E E E E E E E E E
Table I
IIa (continued) Table II It) R8'9 '7 RA Y" m, o, ('
C) Hat E E E E I E E E E E δδδδδδδδδδδδδδδδδzzzzzzI
I E E E I Engineering Engineering I Engineering Engineering I E
E E E E E I E E E E E E
E E E E E E E I E E E E
E E E E E E E I E E E E E
E E E E E E E E E E E E
E E I Engineering Engineering IR10R11R12RA
Y'! J Yugen C) 42CH, HHHA-2H CH2CH3HHHA-3CI C) (2CH3HHHA-4C1 R10RuR12RAX2Y2X3.(OC)-1111---Jidan-11-O'120'13HHHA-5CH2O-1, CH2
0(,--O-12CH,HHHA-5CH20430
(2CF3--CHfH, HHHA-500-120-
1304,--O-12CH38HHA-500-12
0-1,Cl-120-1,--C)(20(38HH
A-500 (P3CH2CF, --CH2043H
HHA-6-+ CCH3-o42CH3HHH
A-6-CH3 N1δδδ6□zzzzzi6z□roδδδkokan1 E
E E E E E E E E E E E E E E E E
z222δδ5δzzzzδzzzz5δδδzzzz 55′? 35δeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee
E E E I E E E I EngNlδδδδ2□
δδ2δδδδδδδ2δδδ2δδδδδδδδδδδ
δOtsuOtsuδδδδ＝ E E E E E E E E
E E E E E E E E E E E E E E E E E E E E E E E E E E Table va (continued) R1112RZX ヱ m
p, <-CI-Co2C1″l, HHNC
M, tJL), R11RL on /-1? RA Nyoyu Gen K R11R12RA X2Y2X' (QC)-
11111 −22110=j6−“ NI δ6δδδδδδδδδ
δδδ1 factory.

5δδδ6δδδδδδδδzzzzδδSelf δxx
xx Engineering I Engineering Engineering I E E E I E E E E E:! :! ! 1 engineering x engineering x
xxxx Engineering Engineering I E E E E E E E E E Exxxxxx Engineering xx E E E E E E I Engineering Engineering I Engineering I Construction table via
(Continued) R13R14R15RZ X Y, 5 Gen HHCH3HCHCH, CH, 219-222R13
R14R15RA two = four - R13R14R1
5RA X2Y2X'm, (QC)-11111111I
u u u u u z z u u u z zI
Q +A I'% M M l'% M
11% +Q M +QI E E E E
E E E E E E E I E E E E I E E E Uuu RoO
uυυroυυ table VII (continued) R26R27ヱ ball l
! 2 and 2 lengths 2 and ΣHCo2C, H, OCH30CH3
CHCM, 0CH30CF2HCH, CHI °0 ”O't) m CI H0CF2HCH3L:?1 Engineering
X E E E E E E
E E2 ω υ υ υ LILILIZZZZZZ
L) ZLIL) Ll υ Preparations Useful preparations of compounds of formula I may be prepared in conventional manner. They criticize powder formulations, X>u formulations, thick emulsion formulations, etc. Many of these items can be used as enclosures.

The spray proboscis can be sprayed in a suitable medium and used at a spray volume of several liters to several hundred liters/hα. High-preservation sesei'+ylJ is mainly an intermediate for the preparation of that porcelain.

It is narrowed as a snout. To describe, the active ingredient is about 0.1~99TJ richness%- and α) blowing ll11 right sex agent about 0
, 1 to 20 and b) solid or deceased body composition field approximately 1 to 99.
At least 1′ of 9%! Contains 1i. Historically, the preparation will contain these ingredients in approximately the following allocation: Table 4 Irrigation Agents 2'0-90 0-74 1-1
0 (including Atsushi Nyuji) 7J'C'l Raw Arp I 1 Te 1 Ri 10-
50 40-84 1-20 powder
1-25 70-99 0-5 granules and new drugs
0.1-95 5-99.9 0-15 High-strength composition 90-99 0-10 0-2* Active ingredient at least 1 gamma occupancy agent or dispersing agent = 100
Of course, there may also be viscous components lower than the table or in the streetcar, depending on the intended use and the nature of the compound. Especially desirable.

It can be coupled by mixing in a water tank or by mixing in a tank.

Crosspiece material [1: J U-body diluent is Watkins (Watki)
n8') et al. "ji," Handbook of I
n5ecticide Dust Diluents a
nd Carrigrs', % 2nd edition, Dorland Books, Catd.
However, pond solids, ie natural and sweet acid solids, may also be used. Hydrating powders and powdered powder are also suitable for dry diarrhea. The crosspiece-like liquid dispersion agent and the 4-medium are Marsden (Mαr
sdgn) person - “Solvgnts c) rbide”
, 42nd edition, Intersig.
nce, N. Y., 11950. A bath purity of 0.1% or less is suitable for a thick suspension agent; a concentrated η agent is preferably stable upon phase separation at 0°C. ”McCutchgorls Dgtgr-ggnt
s and Emulsifigrs AnnaL”
, Allured Publ.
orp, , 7V, J, ).

Sisgly and Wood'
) Author.

``Encyclopedia of' Surfacg
Activg Agencies”.

Chemical Publishing '4i
Co, Inc.

Mk', ) - 1964 shows mosquito notes and their recommended uses. All shrines stand on their own.

A small amount of nitrifying agent may be included to make a cake, pay tribute, and store the live lily of the trading king Zemu.

Methods for manufacturing such compositions are well known.

The composition is manufactured by mixing the gold component into the mixture.

Extractive solid compositions are prepared by blending and usually grinding using a hammer mill or carcass energy mill. -Fjlil preparations are manufactured by wet mill loading [see LittLgr's Rice Painting 3.o No. 60.084]. Granular carriers are preformed with host substances into granules and tablets. It can be prepared by spraying on top or by the vacuum method. See also.

"Agglo-mgration" by J. Browning', Chemic
Al I! J'ngingring, December 4th issue, p. 147 (1967), and Parry''
Chemical Enggr's tia
ndbook.

4th edition, pp. 8-59, McGr.
aw-Hill, N. Y.), 1963.

Further 6. ! , 5jA, see for example the following: 83M, Louz", U.S. 7 Hoken M 3.2
35°361, '5f! J6 愼16 line～Rin7 woodcutter 119
Lines and Practices 10-410 Nott, W. Luckgnbaugh,
U.S. National Register No. 3.309.192, Article 5, lines 43 to 7
Tsu, -62 What and Example 8.12.15.39.41゜5153.5111,132,138-140゜162
~164,166.167.169~182゜B, Sosin CGysin) and &, Knusli (Knusli
).

U.S. Oxen Rabbit 2.891,855 No. 3 Lines 166-5
Wandering 17 and Furikiyama Examples 1-4゜G, C, Tarinoy -7y (Ktingman) 者-'Wg gdContral as a Sign
ce”, Soyoung Willie & Sons (John
Wilgy and 5ons' Inc.

N, Y, ), 1961-pp. 81-96.

J, D, -y Layer CFrygr)'Srbi S, A,:
x, zz:y, x.

(tlvans) d, “Weed C:ontr
ol fiandbook”, 5th edition, Blackwell Scientific Publication 7, c
(Blackwg l l Scint 1ficP
publications, Oxford), 196
8, pp. 101-103.

In the next implementation, 11, all capitals will be in a sleepy summer style where they will not refuse.

1-11ζI N-[(4,6-dimethylpyrimidin-2-yl)ami7carponyll-1 -(1-methylethyl)-LH-imidazole-2-sulfonamide 80% Sodium alkylnaphthalenesulfonate 2 % Sodium ligninsulfonate 2% Synthetic amorphous silica
3% kaolinite
13% of the above ingredients were mixed, hammer milled until all solids were less than 50 microns woody, mixed again and packaged.

N-[(4-methoxy-6-methylpyrimidin-2-yl)ami7carponyl]-1-(1-methylethyl)-1 H-imidazole-2-sulfonamide 50% Al-Naphthalenesulfonate sodium 2 % low viscosity methylcellulose 2% diatom-F,
46% of the above ingredients were mixed, coarsely ground in a hammer mill, and then ground in an air mill to produce particles essentially all less than 10 microns in diameter. The product was mixed again and packaged.

Irrigation agent of R Week Example 28 5% attapul guide particles (US standard sieve No. 20-40, 0.84-0.42 mm) 95% A slurry of the irrigation agent containing about 25% solids was double- The 6 particles sprayed onto the surface of 7 tapalgite particles in a cone mixer were dried and packaged.

N-[(4,6-Simethoxypyrimidin-2-yl)aminocarbonyl]- ■-(l-methylethyl)-1H-gomidan-2-sulfonamide 25% amorphous sodium sulfate 10% crude lignin sulfone Sodium Acid 5% Sodium Alkylnaphthalene Sulfonate 1% Calcium/Magnesium Bentonite 59% 1- Ingredients were mixed, ground in a hammer mill, and moistened with approximately 12% water. The mixture was extruded into a cylinder approximately 3+++ meters in diameter and cut into tablets approximately 3 inches long. It could be used directly after drying, or the dried tablets could be crushed and passed through a No. 20 US standard sieve (opening 0, 84en). Particles that remained on a US Standard Sieve No. 40 (0.42 am opening) were packaged for use and those below were recycled.

N-[(4,6-dimethylpyrimidin-2-yl)aminecarbonyl]-1-ethyl-IH-imidazole-2- sulfonamide 25% polyoxyethylene sorbitol hexaoleate 5% higher aliphatic hydrocarbon oil 70 The ingredients listed below were ground together in a sand mill until all solid particles were about 5 microns or less. The thick suspension produced can be applied directly, but is preferably applied after spreading in oil or emulsifying in water.

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminecarbonyl]-1-ethyl-IH-imidazole-2-sulfonamide 20% Sodium alkylnaphthalenesulfonate 4% Sodium ligninsulfonate 4% Low viscosity Methylcellulose 3% Acpal Guide
69% of the above components were coarsely ground. After milling in a hammer mill to produce particles that were all woody and less than 100 microns in diameter, the material was remixed, passed through a No. 50 US standard sieve (0.3 m+s opening), and packaged.

N-[(4,6-Simethoxypyrimidin-2-yl)aminocarbonyl]-1-ethyl-IH-imidazole-2-sulfonamide 1% N,N
- Dimethylformamide 9% Attapulgide particles (US Standard Sieve No. 20-40) The 90% active ingredient was dissolved in the solvent and the solution was sprayed onto the dedusted particles in a double cone mixer. The mixer was left running for a while after the solution was sprayed and then packaged.

1 skin 1 stop A N-[(4,6-dimethylpyrimidin-2-yl)ami7carponyl]-1-(1-methylethyl)-18-imidazole-2-sulfonamide 40% polyacrylic #concentrated Agent 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% sodium phosphate 0.5% polyvinyl alcohol i,o% water
56.7% The above ingredients were mixed and ground together in a sand mill until all solid particles were about 5 microns or less.

Enseishiyu J Xijun N-, [(4-methoxy-6-methylpyrimidine-2-
yl) ami7carponylco 1-(1-methylethyl)-1 H-imidazole-2-sulfonamide, sodium 11.5% water
95% m was added directly to water with stirring to form a solution, which was packaged for subsequent use.

N ~ [(4,6-simethoxypyrimidin-2-yl)
[aminocarbonyl]-1-(1-methylethyl)-1H-imidazole-2-sulfonamide 0.1% Acpalguide particles (US standard sieve No. 20-40) 9.9.9
% active ingredient is dissolved in the solvent and the solution is double
The dedusted particles were sprayed in a cone mixer. After spraying the solution was complete, the material was warmed to evaporate the solvent. The material was allowed to cool and packaged.

χ惠廻11 Agent - N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-ethyl-IH-imidazole-2- Sulfonamide 80% wet agent 1% crude lignin Sulfone base (5-20% natural sugar content) 10% attapulgite clay 9% The above ingredients were mixed and ground and passed through a No. 100 sieve.

This material was then added to a fluidized bed granulator and a stream of air was applied to gently fluidize the material.

A fine spray of water was then sprayed onto the fluid.

Fluidization and atomization continued until particles of the desired size range were produced. After spraying was stopped, fluidization was continued, with optional heating, until the water content was at the desired level, generally below 1%. The material is then removed and sieved to the desired size range, generally no.
410-149 microns) and packaged for use.

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminecarbonyl]-1-ethyl-IH-imidazole-2-sulfonamide 99% silica aerogel
0.5% synthetic amorphous silica
0.5% - The ingredients listed above are mixed and ground in a hammer mill so that all of the wood grains pass through a US standard sieve 50.
(aperture 0.3+s+a) was produced. This thickener can be further formulated as required.

N-[(4,6-Simethoxypyrimidin-2-yl)ami7carponyl l-ethyl-IH-imidazole-2-sulfonamide 90% Dioctyl sodium sulfosuccinate 0.1% Apricot fine silica 9.9% , mix the components listed in E,
All the solids were ground in a hammer mill until the grain size was less than 100 microns. The material was passed through a No. 50 US standard sieve and packaged.

N-[(4.6-dimethylpyrimidin-2-yl)ami7carbonyl]-1-(1-methylethyl)-1H-imidazole-2-sulfonamide 40% Sodium ligninsulfonate 20% Montmorillo Night clay 40% Mix the listed ingredients and coarsely grind with a hammer mill.

It was then ground in an air mill to produce ligneous particles that were all less than 10 microns in diameter. The product was recombined and packaged.

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminecarbonyl]-1-(1-methylethyl)-1 H-imidazole-2-sulfonamide 35% poly7
Mixture of alcohol carboxylic acid esters and oil-soluble petroleum sulfonates 6% xylene
59% of the above ingredients were mixed and ground together in a sand mill until all solid particles were about 5 microns or less. The products can be applied directly, spread in oil or emulsified in water.

Uses The compound proboscis VI of the present invention is used as a powerful urinary stimulant. They're full of everything else. Areas where a +21 gap is expected, such as around fuel agency tanks, around 1iφ storage, industrial wealth areas, parking lots, outside gates, around billboards, expressways and railway areas before the germination of Usuzaku. And/or use a wide net-circumfered arbor for extermination of germination waves. In addition, one uncombined # is the crop proboscis v1, and the wheat and soybean rice field are 6 singles before 3P' and /
It is also useful for selectively exterminating rh after v'i root buds.

The convenient rate of use of the compounds of the present invention depends on their use as swamp or total herbicides, the coexisting crop species, the species to be controlled, the weather and climate, the formulation chosen, the method of application, the presence of Determined by many factors, including the foot of the leaf. - On a scale of 100 to 100, the present compound 9 should be used once more in 97hα mice from about 0.02 to 10. In this case, earthenware and/or earthenware, sorghum, corn,
Soybean, rice, wheat shoots 2, and spiny stems of Japanese radish were propagated while they were still in full bloom, and when they were harmless to other things, they germinated during quiet periods using Tani and Shida chemicals 6. What happened to the previous lump? At the same time, the cotton of Gomaki's nest (including the cotyledons), the kidney bean with the three leaflets of the third gold, the crabgrass of the second collection, the two-leafed goldenberry, the oat with two leaves, and the three-leafed oat. Leaf of(
Episugusa, four leaves (producing cotyledons)
morning glory, four leaves (including baby tea) of 10,000 sorghum, four leaves of sorghum, west and east corn, two cotyledons of soybean, three leaves of rice, - pear of wheat, and 3 to 5 leaves of east. I spouted the Hamasuge°. The treated fC explants 2 and other control plants were incubated in a wetland for 16 days, then all bales were removed.
Compared to R-Sho V11.

Each of the six treatments was visually reviewed. Evaluation using 1iL
In the LI method, a scale of 0, that is, no effect, was set in km. The accompanying letters and symbols have the following meanings.

C = Kaka / Encouragement D - Fallen leaves L" = Party bud...Stop G = Life growth delay blocking B = Pre-5 to the shadow of the older brother 1β U = Ten' colored thread formation X = Leaf enemy sashihara 6)' = IHd The tumor was formed by this method, and the evaluation of the swollen cut is shown in 4A.For this test, select quickly ='L fζ1 wide excess Irl not 1
In the 19th century, it was found that the first sword that was tested was a 1-year-old sword at the age of 1, this second round of growth, and that it was still alive and early.
Ivy.

Compound 31 CH3.

Compound: Compounds (continued) Compounds (continued) Compounds (continued) ′　Compound (continued) l″′13 Compound (hc) Compounds (continued) LIo engineering 0000000 NK’+ O small.

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Claims (1)

[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is H or CH_3, and Q is ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Q-1, ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼Q-2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼Q-3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼Q-4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼Q -5,
▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-6, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-7, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-8, ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼Q-9 or▲There are mathematical formulas, chemical formulas, tables, etc.▼Q-
10, R_1 is H, C_1 to C_8 alkyl, C_3 to C_6
Alkenyl, C_5-C_6 cycloalkyl, C_5-
C_6 cycloalkenyl, C_3-C_6 alkynyl,
C_4-C_7 cycloalkylalkyl, (R_1_7
CH)nC(O)R_1_6, (R_1_7CH)nC
O_2R_1_8(R_1_7CH)nCOSR_1_
9, (R_1_7CH)nCONR_2_0R_2_1
, (R_1_7CH)nSO_2NR_2_0R_2_
1, (R_1_7CH)nSO_2R_2_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or a) 1 to 3 F, Br or Cl atoms, or b)
C_1-C_6 alkyl substituted with OR_1_6, R_2, R_3 and R_4 are independently H or CH_
3, R_5 is H, C_1-C_4 alkyl, -OR_6, N
O_2, F, Cl, Br, CO_2R_2_4, S(O
) mR_2_5 or SO_2NR_2_0R_2_1
and R_6 is H, C_1 to C_4 alkyl, C_3
~C_4 alkenyl, C_3-C_4 alkynyl, CO
_2R_1_0, SO_2NR_2_0R_2_1, S
O_2R_2_2 or a) 1 to 3 F, Cl or Br atoms, or b) C_1 substituted with OCH_3
~C_4 alkyl, R_7 is H or CH_3, R_8 is H, C_1-C_4 alkyl, -OR_1_6
, NO_2, F, Cl, Br, CO_2R_2_4, S
(O) mR_2_5 or SO_2R_2_0R_2_
1, R_9 is CH_3 or C_2H_5, R_1_0 is H, C_1-C_4 alkyl, C_3-
C_4 alkenyl, C_3-C_4 alkynyl, CO_
2R_2_4, SO_2R_2_0R_2_1 or S
O_2R_2_2, R_1_1 is H, C_1 to C_3 alkyl, F, Cl,
Br, NO_2, -OR_1_6, CO_2R_2_4
, S(O)mR_2_5 or SO_2NR_2_0R
_2_1, R_1_2 is H or CH_3, R_1_3 and R_1_4 are independently H, C_1 to C
_3 alkyl, -OR_1_6, F, Cl, Br, NO
_2, CO_2R_2_4, S(O)mR_2_5 or SO_2NR_2_0R_2_1, R_1_5 is H or CH_3, R_1_6 is C_1-C_3 alkyl, R_1_
7 is H or CH_3, R_1_8 is C_1-C_4 alkyl, C_3-C_4
Alkenyl, C_3-C_4 alkynyl, CH_2CH
_2Cl or CH_2CH_2OCH_3, and R
_1_9 is C_1-C_4 alkyl, C_3-C_4 alkenyl, C_3-C_4 alkynyl or CH_2C
H_2OCH_3, R_2_0 and R_2_1 are independently CH_3 or C_2H_5, R_2_2 is C_1-C_3 alkyl or CF_3, and R_2_3 is H, Cl, Br, CH_3, F, CF_3
, OCH_3 or NO_2, R_2_4 is C_1-C_3 alkyl or allyl, R_2_5 is C_1-C_3 alkyl, m is 0,
1 or 2, n is 0 or 1, R_2_6 is H, C_1-C_3 alkyl or CH_
3C(O)NH, R_2_7 is H, C_1-C_3 alkyl, C_1-C
_3 alkoxy, C_1-C_3 alkylthio or C
_1-C_3 alkoxycarbonyl, R_2_9
is H, C_1-C_3 alkyl, C_1-C_3 alkoxy, C_1-C_3 alkylthio, C_1-C_3 alkoxycarbonyl, NO_2, Cl, Br or CF
_3, R_2_9 is H, Cl or CH_3, R_3_
0 is H, Cl or CH_3, R_3_1 is Cl
, C_1-C_3 alkoxycarbonyl or C_1-
C_3 alkyl, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-1, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-5 or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-6, and X is CH_3, OCH_3, Cl , F, OCF_2H or SCF_2H, and Y is CH_3, C_2H_5, OCH_3, OC_2H
_5, CH_2OCH_3, CH(OCH_3)_2,
OCH_2CF_3, OCF_3, NH_2, NHCH
_3, N(CH_3)_2 or GCF_2T,
where G is O or S and T is H, CHClF, CHBrF, CF_2H or CHFCF
_3, Z is CH or N, Y_1 is H, Cl, CH_3OCH_3 or OCF_
2H, and X_2 is OCH_3, CH_3, CH_2CH_3, S
CH_3 or SCH_2CH_3 and Y_2 is CH_3, CH_2CH_3 or CH_2C
F_3, and X_3 is OCH_3 or CH_3, provided that a) when Q is Q-7, Q-8, Q-9 or Q-10, R is H, and b) The total number of carbon atoms is 8 or more, and c) R_1
is other than C_1-C_3 alkyl, then R_3 is H
d) R_5 is H, CH_3, OCH_3 or NO_2
e) R_6 is CO_2R_1_■, SO_2NR_2_0R_2_1 or SO_2R_2
When _2, R_5 is H, CH_3, OCH_3
f) When R_1_0 is other than C_1-C_3 alkyl, R_1_1 is H, Cl, OCH_3, NO_2 or CH_3; g) One of R_1_3 or R_1_4 is CO_2R_
2_4, S(O)mR_2_5 or SO_2NR_2
When _0R_2_1, the other is H, Cl, CH_
3, OCH_3 or NO_2, h) R_2_9 and R_3_0 are not Cl at the same time, i) when X is Cl or F, Z is CH and Y is OCH_3, NH_2, NHCH_3 or N(CH_3)_2 and j) Q is Q-7, Q-8
, Q-9 or Q-10, A is A-1, X is CH_3, OCH_3 or OCF_2H, and Y
are CH_3, OCH_3, OC_2H_5, OCF_2
H or CH_2OCH_3, and k) When X or Y is OCF_2H, Z is CH] However, in the above formula, R is H and Q is ▲ mathematical formula, chemical formula, table, etc. ▼Q-1, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q-4 or ▲Mathematical formulas, chemical formulas,
There are tables etc.▼Q-5, R_1 is C_2-C_3 alkyl, R_1_0 is C_1-C_3 alkyl, R_1_
1 is C_1-C_3 alkyl, F, Cl, Br or C
O_2R_2_4, where R_2_4 is C_1~
C_3 is alkyl or allyl, and A is ▲Mathematical formula, chemical formula, table, etc.▼A-1, where X and Y are CH_3 or OCH_3, respectively.
and Z is CH or N] and agriculturally suitable salts thereof. 2. Q is Q-1, Q-2, Q-3, Q-4, Q-5 or Q-6, and A is ▲There is a mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula,
There are tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X is CH_3, OCH_3 or Cl, and Y is CH
_3, C_2H_5, OCH_3, OC_2H_5, C
H_2OCH_3, CH(OCH_3)_2, NH_2
, NHCH_3 or N(CH_3)_2, Z is CH or N, Y_1 is H, Cl, CH_3 or OCH_3,
X_2 is OCH_3 or CH_3 and Y_
2. The compound according to claim 1, wherein 2 is CH_3. 3. Q is Q-7, Q-8 or Q-9, and R_2_
6 is H, C_1-C_3 alkyl or CH_3C(O
)NH, R_2_7 is H, C_1-C_3 alkyl, C_1-C
_3 alkoxy, C_1-C_3 alkylthio or C
_1-C_3 alkoxycarbonyl, and R_2_8 is C_1-C_3 alkyl, C_1-C_
3 alkoxy, C_1~C_3 alkylthio, C_1~
C_3 alkylsulfonyl, C_1-C_3 alkoxycarbonyl, NO_2, Cl, Br or CF_3, R_2_9 is H, Cl or CH_3, R_3_
0 is H, Cl or CH_3, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Y is CH_3, OCH_3, OCF_2H, OC_2H
_5 or CH_2OCH_3, X is CH_3, OCH_3 or OCF_2H,
Z is CH or N, provided that (1) R_2_9 and R_3_0 are not Cl at the same time, and (2) X or Y is OCF
When Z is _2H, Z is CH. Compounds according to claim 1 and agriculturally suitable salts thereof. 4. Q is Q-10, R_3_1 is Cl, C_1-C_3 alkoxycarbonyl or C_1-C_3 alkyl, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X is CH_3, OCH_3 or OCF_2H can be,
Y is CH_3, OCH_3, OC_2H_5, OCF_
2H or CH_2OCH_3 and Z is CH or N, with the proviso that when X or Y is OCF_2H, Z is CH. salts. 5. The compound according to claim 1, wherein R is H. 6. The compound according to claim 1, wherein A is A-1 and Z is CH. 7. The compound according to claim 1, wherein Q is Q-1 or Q-6. 8. Herbicidally effective amount of one or more types of claims 1-
An agricultural composition comprising a compound according to paragraph 7 and at least one of the following: (a) a surfactant and (b) a solid or liquid diluent. 9. A method for controlling the growth of undesirable plants, which comprises applying an agriculturally effective amount of one or more compounds according to claims 1 to 7 to the undesirable plant areas. 10, (a) Aminoheterocycle of formula H-N-A is converted to (1) formula Q
Contact the sulfonyl isocyanate of SO_2NCO, or the N-phenylsulfonyl carbamate of formula (2) ▲ ▲ Numerical formula, chemical formula, table, etc. ▼, or (b) contact the sulfonamide of formula QSO_2NH_2 with (1)
In the presence of equimolar amounts of trimethylaluminum, contact with methyl carbamate of formula ▲ ▲ mathematical formula, chemical formula, table, etc. ▼ or (2) formula ▲ mathematical formula, chemical formula, table, etc. ▼ [where X' Cl and Y' is Cl or Br], optionally followed by reaction with a nucleophile such as methoxide or ethoxide ions, or (3) the presence of a base. Below, there are formulas, chemical formulas, tables, etc., which consist of contacting the N-heterocyclic carbamate of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [where R is H or CH_3] , Q has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ Q-1, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ Q-2, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ Q-3, ▲ mathematical formulas, chemical formulas, There are tables, etc.▼Q-4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q-5,
▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-6, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-7, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Q-8, ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼Q-9 or▲There are mathematical formulas, chemical formulas, tables, etc.▼Q-
10, R_1 is H, C_1 to C_8 alkyl, C_3 to C_6
Alkenyl, C_5-C_6 cycloalkyl, C_5-
C_6 cycloalkenyl, C_3-C_6 alkynyl,
C_4-C_7 cycloalkylalkyl, (R_1_7
CH)nC(O)R_1_6, (R_1_7CH)nC
O_2R_1_8, (R_1_7CH)nCOSR_1
_9, (R_1_7CH)nCONR_2_0R_2_
1, (R_1_7CH)nSO_2NR_2_0R_2
_1, (R_1_7CH)nSO_2R_2_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or a) 1 to 3 F, Br or Cl atoms, or b)
C_1-C_6 alkyl substituted with OR_1_6, R_2, R_3 and R_4 are independently H or CH_
3, R_5 is H, C_1-C_4 alkyl, -OR_6, N
O_2, F, Cl, Br, CO_2R_2_4, S(O
) mR_2_5 or SO_2NR_2_0R_2_1
and R_6 is H, C_1 to C_4 alkyl, C_3
~C_4 alkenyl, C_3-C_4 alkynyl, CO
_2R_1_8, SO_2NR_2_0R_2_1, S
O_2R_2_2 or a) 1 to 3 F, Cl or Br atoms, or b) C_1 substituted with OCH_3
~C_4 alkyl, R_7 is H or CH_3, R_8 is H, C_1-C_4 alkyl, -OR_1_6
, NO_2, F, Cl, Br, CO_2R_2_4, S
(O) mR_2_5 or SO_2R_2_0R_2_
1, R_9 is CH_3 or C_2H_5, R_1_0 is H, C_1-C_4 alkyl, C_3-
C_4 alkenyl, C_3-C_4 alkynyl, CO_
2R_2_4, SO_2R_2_0R_2_1 or S
O_2R_2_2, R_1_1 is H, C_1 to C_3 alkyl, F, Cl,
Br, NO_2, -OR_1_6, CO_2R_2_4
, S(O)mR_2_5 or SO_2NR_2_0R
_2_1, R_1_2 is H or CH_3, R_1_3 and R_1_4 are independently H, C_1 to C
_3 alkyl, -OR_1_6, F, Cl, Br, NO
_2, CO_2R_2_4, S(O)mR_2_5 or SO_2NR_2_0R_2_1, R_1_5 is H or CH_3, R_1_6 is C_1-C_3 alkyl, R_1_
7 is H or CH_3, R_1_8 is C_1-C_4 alkyl, C_3-C_4
Alkenyl, C_3-C_4 alkynyl, CH_2CH
_2Cl or CH_2CH_2OCH_3, and R
_1_9 is C_1-C_4 alkyl, C_3-C_4 alkenyl, C_3-C_4 alkynyl or CH_2CH
_2OCH_3, R_2_0 and R_2_1 are independently CH_3 or C_2H_5, R_2_2 is C_1-C_3 alkyl or CF_3, and R_2_3 is H, Cl, Br, CH_3, F, CF_3
, OCH_3 or NO_2, R_2_4 is C_1-C_3 alkyl or allyl, R_2_5 is C_1-C_3 alkyl, m is 0,
1 or 2, n is 0 or 1, R_2_6 is H, C_1-C_3 alkyl or CH_
3C(O)NH, R_2_7 is H, C_1-C_3 alkyl, C_1-C
_3 alkoxy, C_1-C_3 alkylthio or C
_1-C_3 alkoxycarbonyl, R_2_9
is H, C_1-C_4 alkyl, C_1-C_3 alkoxy, C_1-C_3 alkylthio, C_1-C_3 alkoxycarbonyl, NO_2, Cl, Br or CF
_3, R_2_9 is H, Cl or CH_3, R_3_
0 is H, Cl or CH_3, R_3_1 is Cl
, C_1-C_3 alkoxycarbonyl or C_1-
C_3 alkyl, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-1, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-5 or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A-6, and X is CH_3, OCH_3, Cl , F, OCF_2H or SCF_2H, and Y is CH_3, C_2H_5, OCH_3, OC_2H
_5, CH_2OCH_3, CH(OCH_3)_2,
OCH_2CF_3, OCF_3, NH_2, NHCH
_3, N(CH_3)_2 or GCF_2T,
where G is O or S and T is H, CHClF, CHBrF, CF_2H or CHFCF
_3, Z is CH or N, Y_1 is H, Cl, CH_3, OCH_3 or OCF
_2H, and X_2 is OCH_3, CH_3, CH_2CH_3, S
CH_3 or SCH_2CH_3 and Y_2 is CH_3, CF_2CH_3 or CH_2C
F_3, and X_3 is OCH_3 or CH_3, provided that: n) When Q is Q-7, Q-8, Q-9 or Q-10, R is H; b) The total number of carbon atoms is 8 or more, and c) R_1
is other than C_1-C_3 alkyl, then R_3 is H
d) R_5 is H, CH_3, OCH_3 or NO_2
e) R_6 is CO_2R_1_8, SO_2NR_2_0R_2_1 or SO_2R_2
When _2, R_5 is H, CH_3, OCH_3
f) When R_1_0 is other than C_1-C_3 alkyl, R_1_1 is H, Cl, OCH_3, NO_2 or CH_3; g) One of R_1_3 or R_1_4 is CO_2R_
2_4, S(O)mR_2_5 or SO_2NR_2
When _0R_2_1, the other is H, Cl, CH_
3, OCH_3 or NO_2, h) R_2_9 and R_3_0 are not Cl at the same time, i) when X is Cl or F, Z is CH and Y is OCH_3, NH_2, NHCH_3 or N(CH_3)_2 and j) Q is Q-7, Q-8
, Q-9 or Q-10, A is A-1, X is CH_3, OCH_3 or OCF_2H, and Y
are CH_3, OCH_3, OC_2H_5, OCF_2
H or CH_2OCH_3, and k) when X or Y is OCF_2H, Z is CH].