1-(n,n-disubstituted carbamoyl)-3-(n,n-disubstituted sulphamoyl)1,2,4 triazoles

The present invention relates to novel compounds of the general formula (1) given hereinafter, to novel herbicidal compositions of matter containing such compound to a method of pre-weed emergence control of graminaceous weeds'by means of such compounds and to a process for the production of said new compounds*

The present patent application has been divided out from Israeli Patent Application No. 41137־

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Compounds included in ־the invention are those of the general formula

<img file="IL47995A_D0001.tif" />

in which R¹ is alkyl containing 1 or 2 carbon atoms, allyl, 2-methylallyl, prop-2-ynyl, alkoxyalkyl containing 2-4 carbon atoms, haloalkyl containing

1- 4 carbon atoms, 2-haloallyl, 2,3-dihaloallyl or cyclopropyl, R is alkyl containing 2-8 carbon atoms, alkenyl containing 2-8 carbon atoms, alkenyloxyalkyl containing 4-8 carbon atoms (for example allyloxyalkyl or (2-methylallyl)oxyalkyl), haloalkyl containing 2-8' carbon atoms, 2-haloallyl, 2,?^dihaloallyl, cyclopropyl or cyclohexyl, R⁵ is alkyl containing 1-4 carbon atoms, allyl, 2-methylallyl, prop-2-ynyl, alkoxyalkyl . containing 2-4 carbon atoms, haloalkyl containing 1-4 carbon atoms, 2-haloallyl, 2,3-dihaloallyl, cyclonropyl or phenyl containing ! '- 3 halo substituents,

R^ is alkyl containing 1-8 carbon atoms, alkenyl containing

2- 8 carbon atoms, alkoxyalkyl containing 2-8 carbon atoms, 20 alkenyloxyalkyl containing 4-8 carbon atoms (.for example allyloxyalkyl or (2-methylallyl)oxyalkyl), haloalkyl containing 1-8 carbon atoms, 2-haloallyl, 2,3-dihaloallyl, cyclopropyl, or cyclohexyl, or FH and R⁴, together with the nitrogen atom to which they are attached, form a heterocyclic rin״, optionally containing 1-4 lower alkyl (preferably methyl)

־ 2 4

F substituents, 'selected from morpholino, pyrrolidine, 1-piperidyl, hexamethyleneimino and heptamethyleneimino, provided that the total number of carbon atoms in R and

R² together is 3 - 9 inclusive, and when R'⁵ is a radical not containing a phenyl nucleus, the total number of carbon atoms in and R^ together is 2 - 9 inclusive.

Preferably an alkoxy, alkenyloxy or halo substituent in an alkoxyalkyl, alkenyloxyalkyl or haloalkyl radical is attached in a position other than the alpha position,

i.e, is attached to a carbon atom other, than that which is attached to the nitrogen atom of the carbamoyl group -CONR^R² or the nitrogen atom of the sulphamoyl group -SO₂NR^R⁴. Under these circumstances, when R^ is alkoxyalkyl it contains 38־ carbon atoms, when R or

R⁴ is alkenyloxyalkyl it contains 5-8 carbon atoms and when R² or R⁴ is haloalkyl it contains 2-8 carbon atoms.

_ 3 The term ^1,halo” includes chloro, bromo and fluoro . ,in the case of ar aliphatic group,. and/is preferably chloro. The term '׳alkoxy includes alkoxy radicals with 1, 2, 3 .or 4 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy and isobutoxy. The term lower designates an alkyl radical with 1-3 carbon atoms, preferably methoxy or methyl, A preferred value of alkenyloxyalkyl is allyloxyalkyl,, for example allyloxyethyl‘ or 3-allyloxypropyl. Preferred values of alkenyl for .R² and R^ are allyl and 2-methylallyl. ־

The radicals R¹ and R² may be straight or branched chain radicals.

Typical values ofR¹ include, for example, methyl, ethyl, allyl, 2-methylallyl, prop-2-ynyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, chloromethyl,

2- chloroethyl, 2-bromoethyl, 2-fluoroethyl, ?־־chloropropyl,

3- bromopropyl, 4-chlorobutyl, 4-bromobutyl, 2-chloroallyl,

2-bromoallyl, 2,3-dichloroallyl, 2,3-dibroinoallyl and cyclopropyl. . .

Q

Typical values of R include, for example, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.butyl, n-pentyl, .isopentyl, n-hexyl, n-heptyl, n-octyl, allyl, 2-methylallyl, 2-allyloxyethyl, 3-allyloxypropyl, 2-chloroethyl', 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-brono propyl, ί

f * יי

4׳ '

4-chlorobutyl, 4-bromobutyl, 5־־^cbloropentyl, 6-chlorohexyl,

2-chloroallyl, 2-bromoallyl, 2,3-dichloroallyl, 2,3dibromoallyl, cydlopropyl״ and cyclohexyl,

2 Typical values of the carbamoyl group -COUR R include dialkylcarbamoyl [for example N-methyl-N-ethylcarbamoyl, diethylcarbaraoyl, N-ethyl-N-propylcarbamoyl, N-ethyl-Nisopropylcarbamoyl, N-butyl-N-ethylcarbanoyl], diallylcarbamoyl, N-allyl-N-alkylcarbamoyl wherein the alkyl radical contains

1- 6 carbon atoms [for example N-allyl-N-methylcarbamoyl,

N-allyl-N-ethylcarbamoyl, N-allyl-N-propylcarbamoyl, ΙΓ-allyl-N-n-butylcarhamoyl, N-allyl-N-isobutylcarbamoyl, N-allyl-N-n-pentylcarbamoyl and N-allyl-N-n-hexylcarbamoyl], N-allyl-N-(2-methoxyethyl)carbamoyl, N-allyl-N-(2-ethoxyethyl)carbamoyl, M-allyl-N-(2-chloroethyl)carbamoyl,

N-alkyl-N-(2-methoxyethyl)carbamoyl or N-alkyl-N-(2st ethoxyethyl)carbamoyl wherein the alkyl radical contains

2- 6 carbon atoms [for examnle N-ethyl-N-(2-methoxyethyl)- j carbamoyl, N-propyl-N-(2-methoxyethyl)carbamoyl, N-etbylN-(2-ethoxyethyl)carbamoyl, and N-propyl-N-(2-ethoxyethyl) carbamoyl], N-methyl-N-cyclohexylcarbamoyl, N-propyl-N-prop¹ 2-ynyl, N-alkyl-N-(2-chloroallyl)carbamoyl wherein the alkyl radical contains 2-6 carbon atoms and N-alkyl-K-(2,3dichloroallyl)carbamoyl wherein the alkyl radical contains 2-6 carbon atoms, N-cyclopropyl-N-propylcarbamoyl, and

N-cyclopropylrN-ethylcarbamoyl.

. The radicals and R^ may be straight or branched chain radicals.

_

J *

׳ 4 ־' ׳

ד

Typical values of R include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.butyl, allyl, 2-methylallyl, prop-2-ynyl, methoxymethyl,

2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, chloromethyl,

2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, J-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 2-chloroallyl, 2-bromoallyl, 2,3-dichloroallyl, 2,3-dibromoallyl, cyclopropyl,.4-chlorophenyl, 4-bromophenyl and 4-fluorophenyl.

Typical values of R^ include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, allyl,

2- methylallyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-n-butoxyethyl, 3-methoxypropyl, J-ethoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-n-

15. butoxyethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl,

3- chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl,

5-chloropentyl, 6-chlorohexyl, 2-chloroallyl, 2-bromoallyl,

2,3-dichloroallyl, 2,3-dibromoallyl, cyclopropyl, cyclohexyl, 2-allyloxyethyl and 3-allyloxypropyl.

. 20 As hereinbefore mentioned, when the group NR^R^ is a heterocyclic group, it may contain 1-4 lower alkyl (preferably methyl) substituents. Such alkyl-substituted heterocyclic groups include, for example, 2,6-dimethylmorpholino, 4-methyl-l-piperidyl, 2-methyl-l-piperidyl and 2,6-dimethyl-l-piperidyl. .

׳Typical examples of the sulphamoyl group -SOgNR^R^

- . . , . 1' i

I include, for example, dimethylsulphamoyl, diethylsulphsmoyl, dipropylsulphamoyl,’ di-n-butylsulphamoyl, diallylsulpnamoyl, , di2)״~methylallyl)sulphamoyl, N10״wer alkyl-N-cyclohexylsulphamoyl for example N-metbyl-N-cyclohexylsulphamoyl,

N-allyl-N-alkylsulphamoyl wherein the alkyl radical contains

- 5carbon atoms (for'example N-allyl-N-methylsulphamoyl, N-allyl-N-ethylsulphamoyl and N-allyl-N-propylsulphamoyl), N-methyl-N-alkylsulphamoyl wherein the alkyl radical contains 1-8 carbon atoms (for example N-rnethyl-N10 ethylsulphamoyl, N-methyl-N-propylsulphamoyl, N-methylN-n-butylsulphamoyl, N-methyl-N-sec.butylsulphamoyl and N-methyl-N-isobutylsulphamoyl), N-ethyl-N-propylsulphamoyl, N-ethyl-N-isopropylsulphamoyl, N-ethyl-N-butylsulphamoyl, N-:n1ethyl-N-(4-fluorophenyl)sulphamoyl, morpholinosulphonyl,

1-pyrrolidinylsulphonyl, 1-piperidylsulphonyl, hexamethyleneiminosulphonyl and heptamethyleneiminosulphonyl. .

t

Preferably, R¹ is alkyl containing 1 or 2 carbon atoms, allyl, 2-methylallyl, prop-2-ynyl* or alkoxyalkyl containing

9 ״

2- 4 carbon atoms and R is alkyl containing 2-8 carbon atoms, allyl or 2-methylallyl. It is preferred that the carbamoyl group COMR R ,is dialkylcarbamoyl in which the alkyl groups are the same or different and together contain

3- 6 carbon atoms, diallylcarbamoyl., N-allyl-N-alkylcarbamoyl. in which the alkyl group contains 1-4 carbon atoms, or N-alkyl-N-alkoxyalkylcarbanoyl in which the alkyl group contains 2 to 4 carbon atoms and the alkoxyalkyl group contains 3 4 ?נס carbon atoms.

Preferably, R³ is alkyl containing 1-4 carbon atoms, allyl, 2-methylallyl, alkoxyalkyl containing 3 or 4 carbon atoms, phenyl containing a single halosubstituent and R^ is 15 ' alkyl containing 1-8 carbon atoms, allyl, methylallyl or alkoxyalkyl containing 3-8 carbon atoms. It is preferred that the sulphamoyl group is dialkylsulphamoyl in which the alkyl groups are the same or different and each contain 1-4 carbon atoms, diallylsulphamoyl, di-(2-methylallyl)sulphamoyl, or N-allyl-N-alkylsulphamoyl in which the alkyl group contains 1-4 carbon atoms.

Especially suitable compounds of formula I) ׳ are ־those in which: . ־ / (a) the carbamoyl group is diallylcarbamoyl and. the sulphamoyl group is dialkylsulphamoyl, di-(2-methylallyl)sulphamoyl or N-allyl-Nalkylsulphamoyl, (b) the carbamoyl groun is dialkylcarbamoyl and the sulphamoyl group is dialkylsulphamoyl, diallylsulphamoyl or H-allyl-N-alkylsulphamoyl,.

(c) the carbamoyl group is N-allyl-N-alkylcarbamoyl and the sulphamoyl group is d!alkylsulphamoyl diallylsulphamoyl or N-allyl-K-alkylsulphamoyl, (d) the carbamoyl groun is N-alkyl-N-alkoxyalkylcarbamoyl and the sulphamoyl group is dialkylsulphamoyl, diallylsulphamoyl or N-allyl־׳Nalkylsulphamoyl

־

The present invention also provides herbicidal conpositions which comprise as an active ingredient a compound of the general formula II in association with a diluent or carrier. The diluent or carrier may be a solid or liquid, 5 optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.

According to a further feature of the present invention there is provided a method for the pre-weed emergence control 10 of graminaceous weeds which comprises applying to the locus of the weeds, for example the soil, a compound of the general formula I A particular embodiment of this feature is a method for the selective pre-weed emergence control of graminaceous weeds such as barnyard grass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), yellow, foxtail or (Setaria lu^escens),/Johnson grass (Sorghum halenense), in a crop area which comprises annlying to the crop area a compound of the general formula II at an application rate sufficient to control the weeds but substantially non-phytotoxic to the crop.

-ΙΟA

Table I

<td colspan="2" rowspan="2"> Compound Γ</td><td colspan="8"> Minimum rate (lb./acre)</td>

<td colspan="4"> Control</td><td colspan="4"> Phytotoxicity</td>

<td> so₂nr⁵r⁴</td><td> C0NR¹R²</td><td> CG</td><td> BG</td><td> YF</td><td> JG</td><td> M</td><td> CO</td><td> Sh</td><td> P</td>

<td> /Me N cyclohexyl</td><td> N(allyl)₂</td><td> 1 5</td><td> 1 Zf</td><td> 1 ־4</td><td> 1 2</td><td> 2</td><td>^&gt;8</td><td> &gt;8</td><td> &gt;8 1</td>

<td> NEt₂</td><td> II</td><td> 1 2־5</td><td> 1 32</td><td> 1 32</td><td> 1 52</td><td> 2</td><td> 4</td><td> 4</td><td> &gt;8</td>

<td> N(Pr)Bu</td><td> 11</td><td> 1 8</td><td> 1 2</td><td> 1 2</td><td> 1 2</td><td> 2</td><td> 2</td><td> 2</td><td> 4</td>

<td> N(Me-allyl)₂</td><td> 1!</td><td> 1 16</td><td> 1 16</td><td> 1 4</td><td> 1 2</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td> pyrrolidino</td><td> rt</td><td> •1 8</td><td> rH| CO</td><td> 1 8</td><td> 1 16</td><td> 4</td><td> 2</td><td> 4</td><td> &gt;8</td>

<td> * N(s-Bu)Me </td><td> 11</td><td> 1 8</td><td> 1 32</td><td> 1 52</td><td> 1 2Γ</td><td> 1</td><td> 4</td><td> 4</td><td> &gt;8</td>

<td> morpholino</td><td> 11</td><td> 1 2</td><td> 1 2</td><td> 1 4</td><td> 1 4</td><td> 4</td><td> &gt;8</td><td> 4</td><td> &gt;8</td>

<td> NEt₂</td><td> N ^s cyclohexyl</td><td> 1 16</td><td> ׳ ג 16</td><td> 1 8</td><td> 1 2</td><td> 4</td><td> &gt;8</td><td> 4</td><td> &gt;8</td>

<td> N( allyl)Me</td><td> N(allyl)Et</td><td> 1 2־3</td><td> 1 32</td><td> 1 52</td><td> 1 8</td><td> 2</td><td> &gt;8</td><td> 2</td><td> &gt;8 j</td>

Tabic I (continued)

<td colspan="2"> so₂nrV</td><td> 2 ו coNirrr</td><td> CG</td><td> EG</td><td> YF</td><td> JG</td><td> M</td><td> CO</td><td> SB</td><td> P</td>

<td></td><td> N(Me)Bu</td><td> /־Pr N \prop-2-ynyl</td><td> 1 4</td><td> 1 4</td><td> 1 6נ</td><td> 1 16</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td> piperidyl</td><td> N(allyl)Pr</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 4</td><td> 4</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td></td><td></td><td> 16</td><td> . 8</td><td> 16</td><td> 8</td><td></td><td></td><td></td><td></td>

<td></td><td> N(allyl)₂</td><td> N(2-methyl allyl)₂</td><td> 1 8</td><td> r-l|CC</td><td> 1 8</td><td> 1 4</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td> N(CH₂CH₂0Et)₂</td><td> NEt₂</td><td> 1 4</td><td> 1 4</td><td> 1 4</td><td> 1 4</td><td> 1</td><td> &gt;8</td><td> 2</td><td> &gt;8</td>

<td></td><td> /Et N *־ cyclopropyl</td><td> N(allyl)₂</td><td> 1 4</td><td> 1 4</td><td> 1 4</td><td> 1 4</td><td> 4</td><td> 2</td><td> 1</td><td> 2</td>

<td></td><td> /Et N ^x 2-all‘yloxyethyl</td><td> 11</td><td> 1 4^-</td><td> 1 4</td><td> 1 4</td><td> 1 4</td><td> 4</td><td> 1</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td> /Pr N ''2 י-chloroally:</td><td> II</td><td> 1 4</td><td> 1 8</td><td> 1 8</td><td> 1 8</td><td> &gt;8</td><td> 4</td><td> 4</td><td> &gt;8</td>

<td></td><td></td><td>_zPr</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> NEt₂</td><td> N '^Kpror)-2-ynyl</td><td> 1 8</td><td> 1 4</td><td> 1 8</td><td> 1 2</td><td> 4</td><td> 4</td><td> 4</td><td> &gt;8</td>

<td></td><td> NEt₂</td><td>_zPr N ^ch₂ch₂c1</td><td> 1 2</td><td> 1 2</td><td> 1 2</td><td> 1. 4</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td> N(allyl)₂</td><td>_zEt N ''2-chloroallyl</td><td> 1 16</td><td> 1 8</td><td> 1 8</td><td> 1 2</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

Table I. (continued)

<td> 5 4 SCLNJTR ά</td><td> 1 2 CONR R</td><td> CG</td><td> BG</td><td> YF</td><td> JG</td><td> M</td><td> C°</td><td> SB</td><td> P</td>

<td> NEt₂</td><td> zPr N</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;⁸</td>

<td></td><td> \CH₂0Me</td><td> 8</td><td> 8</td><td> 8</td><td> 8</td><td></td><td></td><td></td><td></td>

<td></td><td> ✓ Et</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> NEt₂</td><td> N x(CH₂)^0Me</td><td> 1 8</td><td> 1 8</td><td> 1 £ .</td><td> 1</td><td> 2</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td> / Et</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> N(allyl)₂</td><td> N ^(CH₂)₅0Me</td><td> 1 16</td><td> 1 4</td><td> . 1 8</td><td> 0נ. |t-׳</td><td> 2</td><td> 2</td><td> &gt;8</td><td> &gt;8</td>

<td> N(allyl)Hex</td><td> N(Pr)Et</td><td> 1 2</td><td> 1 2</td><td> 1 2</td><td> 1 2</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;₈</td>

<td> /Me N</td><td> /Me N</td><td> 1</td><td> '־1</td><td> 1</td><td> 1</td><td> &gt;8</td><td> 4</td><td> &gt;8</td><td> &gt;8</td>

<td> 4-fluorophenyl</td><td> * cyclohexyl</td><td> 16</td><td> 16</td><td> 16</td><td> 5־1</td><td></td><td></td><td></td><td></td>

<td> N(Me)Bu</td><td> N(Me)Hex ״</td><td> 1 ־4</td><td> 1 2</td><td> 1 4</td><td> 1 4</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td> NEt״</td><td rowspan="2"> N(i-Pr)Et</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1'</td><td> &gt;8</td><td> 2</td><td> &gt;8</td>

<td> 2</td><td> 6־1</td><td> 16</td><td> 15</td><td> 6־1</td><td></td><td></td><td></td><td></td>

<td> N(allyl)₂</td><td> N(Et)Pen</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 4</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td></td><td></td><td> 8</td><td> 4</td><td> 16</td><td> 8</td><td></td><td></td><td></td><td></td>

<td></td><td> z Et</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> NE%</td><td> N</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td> 2</td><td> (CH₂)₂0Et</td><td> 4</td><td> 8</td><td> 2</td><td> 2</td><td></td><td></td><td></td><td>¹</td>

<td> N(allyl)₂</td><td> N(allyl)Me</td><td> 1 6־1</td><td> 1 16 :</td><td> 1 6־1</td><td> 1 6־1</td><td> 1</td><td> 2</td><td> 4</td><td> &gt;8</td>

<td> piperidyl</td><td> ' Pr ^Ns(CH₉0(״Me c. “</td><td> 1 6־1</td><td> 1 6־1</td><td> 1 6־1</td><td> 1 6־1</td><td> &gt;8</td><td> &gt;8</td><td> 4</td><td> &gt;8</td>

<td> N(allyl)₂</td><td> NEt₂</td><td> 1 6־1</td><td> 1 ־ 5־1</td><td> 1 2־3</td><td> 1 52</td><td> 1</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

<td> hexamethyleneinimo</td><td> N(allyl)₂ *</td><td> 1' ־4</td><td> 1</td><td> 1 4</td><td> 1 ־4</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td><td> &gt;8</td>

יי 1 ־ . . י \!q have found that the compounds of the present invention have superior herbicidal properties το a variety of closely related 1,2,4-triazolcs within the hereinbefore defined broad group of compounds described 5 in United States Patent Specification No. 3,308,131, ’ including a representative selection of the compounds ! specifically exemplified in that specification.

For purposes of comparison, various 1,2,4־־ triazoles i within the scope of the isomeric formulae A but outside the scope of the compounds of the invention were included in the qQ glasshouse trials described above, using application rates logarithmically reducing from 32 lb./acre. The results obtained are given in the following Tables 3 and 4 in.which ״* designates a compound that is specifically exemplified ; in United States Patent Specification No, 3,508,131. The ! 15 compounds that gave no control of any of the weeds crabgrass, ί

I barnyard grass, yellow foxtail and Johnson grass at the maxi— mum application rate of 32 lb,/acre are listed in Table 4.

j

I In view of their lack of activity against the weeds, these compounds were not included in the crop tests. Of the ) 20 compounds listed in Table 4 those that arc believed to have ί been obtained as a mixture of isomers (corresponding to formulae A) containing appreciably 5>הד10מ than 10/ of each ! isomer, or those in which the isomeric structure is uncertain, ί ‘ .

j are designated 1(2)- in the nomenclature of the carbamoyl i 25 group. The remaining compounds are believed to have been j obtained substantially as the isomer given, or predominantly as this isomer with less than 10/ of the other isomer.

? Table II

<td colspan="3"> Compound</td><td colspan="8"> Minimum rate (lb./acre)</td>

<td></td><td> (1, x-0,</td><td> !Ah)</td><td colspan="4"> . control</td><td colspan="4"> phytotoxicity</td>

<td></td><td> R⁷</td><td> )»⁵R⁶</td><td> CG</td><td> BG</td><td> YR</td><td> JG</td><td> CO</td><td> SB</td><td> M</td><td> P</td>

<td> *</td><td> Me</td><td> lff4e₂</td><td> 1</td><td> 16</td><td> 2</td><td> 2</td><td> 4</td><td> 8 .</td><td> 4</td><td> 8 .</td>

<td></td><td> Cl</td><td> ii</td><td> 4</td><td> ' 2</td><td> 2</td><td> ־2</td><td> 2</td><td> 4</td><td> 2</td><td> 4</td>

<td> *</td><td> Br</td><td> If</td><td> 4.</td><td> 4</td><td> 32</td><td> 4</td><td> 1</td><td> 1</td><td> 2</td><td> 4</td>

<td> *</td><td> SMe</td><td> מ</td><td> 1</td><td> 4</td><td> 4</td><td> 2</td><td> ' roll-׳</td><td> 2</td><td> 2</td><td> 2</td>

. ί .'t

Table י . .

Com pou ן; ק n w .ו t h 10(1׳ fo 1 10 ^-.75,11.4 siibnti Luon •0 on the j 2 /,-triazolc riiii'^1- gave no wc!?tl eontro.1. at 52 Ib./acrc.

* l-diincthylcarbamoyl .' ' . 5 ' * 1-dimethylthiocarbam.oyl j 1(2)-dimethylthiocarbamoyl-3-ethylthio

1(2)-diethylthiocarbamoyl-3-ethylthio j * l(2)-dimethylthiocarbamoyl-3~methylthio-5-rcethyl ; . « . 1(2)-dimethylcarbamoyl-3-methylsulphonyl-5-methyl

;. !2)1 * ס )-oiethylcarbamoyl-5-methylthio-5-methyl * l(2)-K-mcthyl-N-n-butylcarbamoyl-3-methylthio-5-methyl ! . ' l(2)-dirasthylcarbar״oyl-5-ethylthio-5-methyl * l~dimethylcarbamoyl-3~dodecylthio-5-n1ethyl . ' i . l-dimethylcarbamoyl-J-n-hexylthio : 15 . l-dimethylcarbamoyl-3-cyclohexylthio ., .

’ ‘ . ' l-dimethylcarbamoyl-3-dodecylthio * l-dimethylcarbamoyl-3-undecyl-5-methylthio ^! l-dir״ethylcarbamcyl-3-benzyl ) * l-dimethvlcarbamoyl-3-benzylthio-5-n;ethyl t

j . 20 . * l״dimethylcarbamoyl-3-phenyl-5-sethylthio : ׳ *. l-dimethylcarbamoyl“3-p-nitrophenylthio-5-1nethyl ׳ l-dimethylcarbamcyl-3-(2,4-dinitrophenylthic׳) * l-di1r.ethylcarbamoyl-35_׳-dimethyl * l-dimethylcarbamoyl-3-(2“diethylaciinoethylthio)-5- /25 ־ methyl .

- lo ' ί

Table substituents on 1,2,4-triazole ring * l-dimethylcarbamoyl-S-ethoxycarbonylmethylthio^ methyl * l-dimethylcarbamoyl-3-(l-dimethylcarbamoyl-l,2,41 triazole * l-(4-methylpiperidinocarbonyl) j * l(2)-pyrrolidinocarbonyl-3-methylthio-5-methyl : l-piperidinocarbonyl-3-ethylthio • 10 l(2)-(4־methylpiperazinocarbonyl)-3-ethylthio

1-(1,2,3,4-tetrahydroquinolinocarbonyl)-3-ethylthio

1(2)-(N-methyl-N-methoxycarbamoyl)“3-ethylthio 1-diallylcarbamoyl l(2)-diallylcarbaii10yl-3־®thylthi0“5-methyl ! 15 l-diallylcarbamoyl-3-(2-diethylaminoethylthio) .

l-diallylcarbamoyl-3-methoxycarbony line thyl

1-di(cyanomethyl)carbamoyl-3-ethylthio i

j The results given above show that the compounds listed | in Table 1 ' are markedly superior to the compounds

1' 20 listed in Tables 2. and 3 in respect of their high level ; of selective pre-emergence activity against all four of j the weeds crabgrass, barnyard grass, yellow foxtail and j Johnson grass in the crops cotton, soyabean, peanut and maize, especially in the crops cotton, soyabean and peanut. . * .

- •17 φ ^: It can be seen from the foregoing description that the compounds of the present invention are of value for the pre-weed emergence control of graminaceous weeds in a variety of crops, for example cotton, leguminous crops such as soyabean and peanut, and cereals such as maize. However., ..it will be appreciated that the individual compounds of the present invention are not all equivalent, in their level of herbicidal activity and selectivity • characteristics. Accordingly the optimum compound for one * —“ particular use'is not necessarily the optimum compound for another particular use.

Insecticidal and miticidal tests have been carried out with a variety of compounds of the present invention, The compounds tested were found to have little or no activity against insects, for example Plutella maculipennis, Phaedon cochlearieae, and aphids such as Aphis fabae and Megoura viciae. The compounds tested were also found to . have little or no activity against mites, for example Tetranychus urticae,. . ' * Regarding the mammalian toxicity of the compounds of the present invention, acute oral toxicity studies in mice have given satisfactory results. In these studies, the compounds of the present invention have been found to be less toxic than certain closely related l,2,״4־triazoles, . 25 for example l-dimethylcarbamoyl-3-methylthio-l,2,4triazole. . '

־. . .- 48 Preparation of compounds of formula I

The compounds of formula IT may be prepared by the hereinafter described processes, which are analogous to known processes for preparing similar compounds.׳

One such process comprises reacting a sulphamoyltriazole of the general formula.

r⁵r⁴no₂s

N----NH

<img file="IL47995A_D0002.tif" />

(VIII) in which R⁵ and R⁴ are as hereinbefore defined for formula I , 1 2 with a carbamoyl halide of the general formula Z-CONR R (IX) in which R and R are as hereinbefore defined ror־

י♦ formula I and 2 is chlorine, lluorine . or bromine,| preferably chlorine. The reaction is suitably effected inI the nresence-of an inert organic liquid as the reaction|

-pl medium, which is preferably a solvent for the reactants.I > 'Ί

It is preferably carried .out at a temperature of from 0 ח π4 to 200 0., for example from 15 to 120 0, Advantageously the reaction is effected in the presence of a suitable?i

ן acid-binding agent, for example a tertiary amine such as| triethylamine or pyridine, in order to' absorb the hydrogen. | jlq, halide produced in the reaction. In an alternative . -$ procedure, the triazole of the general formula VIII may be 'יי converted to an alkali metal (for example sodium) salt thereof prior to the reaction with the carbamoyl halide. The alkali metal salt may be obtained by reacting the triazole of the general formula VIII with an alkali metal hydride, amide or alkoxide, in accordance with known methods.

The carbamoyl halides of the general formula IX may by prepared by reacting a secondary amine of the general

12 formula ΗΝΉ R , in which R and R are as defined above, with a carbonyl halide COZ₂, in accordance with known methods.

The compounds of formula I may also be prepared by a process which comprises reacting a carbamoyl halide of the general formula —״ N-COZ

AW -J J ^(x) in which R׳’, and Z are as defined for formula II, with a secondary amine of the general formula HNR R־, in which

R־⁵־ and R² are as defined for formula If. The reaction is suitably effected in the presence .of an inert organic ׳ liquid as the reaction medium, which is preferably a solvent for the reactants. It is preferably carried out at a temperature of from-20 to 100%., for example from 0 to 40%. Advantageously the reaction is effected in the presence of a־suitable acid-binding agent, for example.a tertiary amine such as triethylamine or pyridine.

XO The carbamoyl halides of general formula X may be prepared from the triazoles of general formula VIII by reaction with a carbonyl halide COZ₂, preferably phosgene, in accordance with known methods.

The sulphamoyltriazoles of the general formula VIII ' (with the exception of NR⁵R⁴ - dimethylamino or 1-piperidyl), are novel compounds. The compounds may be prepared by a process which comprises reacting a l,2,4-triazole-3־sulphonyl halide, preferably 'the chloride, with an amine of the general formula HNR^R⁴ (XI). The reaction may be effected in an aqueous medium, or in a suitable inert organic liquid,

״.;., which is ureferably a solvent for the reactants, Riethyl

Ϊ . *’ ^J ether and tetrahydrofuran are examples of suitable inert organic liquids that in many instances are solvents for (,he reactants. The reaction is preferably effected in the presence of a suitable acid-binding agent, for example 3 4 triethylamine or an excess of the amine HNR R , in order to absorb the hydrogen halide produced in the reaction.

־

The reaction is suitably effected at temperatures in the range 10 - 30°C, . ' .

The compounds of the prose^t^invention may also be prepared by _a .process which comprises reacting a carbonylbistriazole of the general formula

<img file="IL47995A_D0003.tif" />

. 3 4 in which R and R are as defined for formula II, with a

1 secondary amine of the general formula HUR R , in which R and R' are as defined for formula II. The reaction is suitably effected in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the ׳'It is preferably carried out at a temperature of reactants, from -20 to 100°C., for example from 0 to 40°C.

The carbonylbistriazoles of the general formula XII may be prepared by reacting a triazole.of the hereinbefore defined general formula VIII with about 0.5 molecular proportions of a carbonyl halide COZ,,, preferably phosgene, _s in accordance with known methods. The reaction is preferably effected in the presence of a suitable acid-binding agent, for example pyridine. After formation of the carbonylbistriazole, it is often convenient to react it, without isolation, with the amine of general formula ר

HNR R .

It will be appreciated by those skilled in the art that the triazoles represented by the general formula VIII are tautomeric and that, for convenience, general formula VIII depicts the structure of one tautomer.

It will be appreciated by those skilled in the art , \ that the acylation reactions described above in the preparations of compounds of formula 1' can theoretically give two isomeric products, one (hereinafter referred to as 1-isomer) having the general formula I and the other (hereinafter.referred to as 2-isomer) having the general formula COURSE² —N R³R⁴NO״S-^^ J .It is believed that the solid compounds of formula I , 10 ־ after, purification by standard methods such as crystallization, are obtained as substantially pure 1-isomer. The liquid compounds of formula. I , as isolated by standard methods such as distillation in vacuo, are believed to be obtained as components of an isomeric mixture consisting predominantly of the 1-isomer together with a minor propertion, generally less than about 10$ of 2-isomer.

' ־ ־ . ί φ In the Examples the following abbreviations are־ used :

Me = methyl, Et = ethyl, Pr -- propyl, Bu = butyl,

Pen = pentyl, Hex = hexyl, i ״ iso and s'־־ secondary. Alkyl radicals without the designation i- ors- signify normal radicals.

In the tabulated compounds the physical constant for a solid compound is its melting point, for an oil the physical constant is the refractive index of the compound since no boiling point was measurable in such instances and, where available, a GLC assay value ($) is quoted in brackets after the refractive index to give an indication of the purity of the oil. For a liquid compound the physical constant is the \ boiling point at the stated pressure (mm. Hg).

The following Examples illustrate the invention.

1.

This Example illustrates the preparation of a compound * of formula .1’ .

A mixture of 6.9 g. 3-diallylsulph'amoyl-l,2,4-triazole,

4.5 g. diethylcarbamoyl chloride,. 6 ml, triethylamine and 25 ml. dry tetrahydrofuran was refluxed under anhydrous־ conditions for 1,5 hours. The cooled reaction mixture was filtered to remove triethylamine hydrochloride and the filtrate was evaporated to remove solvent. The solid residue was recrystallized from petroleum ether, b.p.

- 80°C., to give l-diethylcarbamoyl-3-diallylsulphamoyl-

1,2,4-triazole, m.p. 49 - 51°C. Elemental analysis satisfactory.

^y The novel intermediate 3-diallylsulphamoyl-l,2,4“triazole was 15repared in the following way. A stream of chlorine was passed into a solution of 20.2 g. l,2,4~triazole-3-thiol in 330 ml. 2N hydrochloric acid, maintaining the temperature of mixture at 0 to -2°C. by means of external cooling. When

<img file="IL47995A_D0004.tif" />

־ j

excess chlorine was present (after 1.5 hours) the solid product was collected by filtration, washed with water, and sucked as dry .as possible on a sudtion filter. There was thus obtained 1,2,4-triazole-3-f5ulphonyl chloride in the form of a damp solid, which was used immediately in the next stage of the preparation. This damp solid was gradually added to a stirred solution of 48.5 g. diallylamine in 100 ml. water, maintaining the temperature of the reaction mixture at 20°^. The reaction mixture was allowed to stand at 20°C. for 20 minutes, and was then acidified to pH 4.0 with concentrated hydrochloric acid. The resulting solid product was collected by filtration, washed with water, and recrystallized from water to give 3-diallylsulphamoyl-l,2,4triazole, m.p. 131 135° ־C. Elemental analysis satisfactory. EXAMPLE 2 .

This Example illustrates the preparation of compounds of formula I .

By reacting the appropriate carbamoyl chloride with the anpronriate 3-sulphamoyl-l,2,4.*triazole in an analogous manner to that described in Example 1. the following compounds were prepared.

*

<td> 2 ו</td><td> t ר</td><td></td><td></td>

<td> ד. rt י! ,</td><td> NrR^f</td><td></td><td> Constant</td>

<td></td><td></td><td> state</td><td> /</td>

<td> S(allyl)₂</td><td> . ^ffis2</td><td> solid .</td><td> ; ׳ . ./58</td>

<td> :(iis)Bu</td><td> ^θ2</td><td> . liquid</td><td> 191-195/./0.5 b.</td>

<td></td><td> morpholino</td><td> .solid ,</td><td> 113 - 114°C. י . </td>

<td> K(allyl)₂_ .</td><td> piperidino</td><td> solid</td><td> 72 - 75°C. '</td>

<td> H{Ee)3n</td><td> piperidino</td><td> solid</td><td> ν ׳, ׳ ./70-71</td>

<td> H(a.lyl)?r .</td><td> piperidino</td><td> . oil ,. </td><td rowspan="2"> ¾⁵1.519 108 - no°c.</td>

<td> +י־ץ .</td><td> piperidino</td><td> solid</td>

<td> h(oyclohexyl)i׳e</td><td> piperidino</td><td> • ,solid</td><td> 117-118⁰¢. ' ¹</td>

<td> n(allyl)it</td><td> piperidino</td><td> solid</td><td> ''50 - 52/. n</td>

<td> h:allyl)₂</td><td> H(allyl)₂</td><td> oil</td><td> n_D²¹ 1.5226 ' ¹</td>

<td></td><td> N(allyl)₂</td><td> ־ solid</td><td> 49 - 51°C.</td>

<td> Hicyclonexylfe</td><td> N(allyl)₂ ' '</td><td> solid</td><td> 55-56¾.</td>

<td> ״(aalyl)Ex</td><td rowspan="2"> N(allyl)₂ . Et₂</td><td> solid</td><td> ' י', ‘W - Λ</td>

<td> i(allyl)₂ ; . .</td><td> solid</td><td> 62 - 65°C.</td>

<td>^St2 ' </td><td></td><td> solid .</td><td> ׳ ./105</td>

<td> H(«yclohexyl)Ke</td><td> '</td><td> solid</td><td> 85 - 85/.</td>

<td> X(allyl)Pr</td><td></td><td> solid</td><td> 31 - 35/,</td>

<td> :felyl)₂</td><td> pyrrolidinyl</td><td> solid </td><td> 67 - 68/.</td>

<td> i'(cycl0i1exyl)!'e</td><td> pyrrolidinyl</td><td> solid</td><td> 109 -110/.</td>

<td>^K2</td><td> pyrrolidinyl</td><td> • solid</td><td> 87 - 88/.</td>

<td> H !!.?) Bn־i</td><td> pyrrolidinyl</td><td> solid־</td><td> 75 -</td><td> 'ίΛ',.</td>

<td> M(allyl)Pr</td><td> pyrrolidinyl</td><td> solid</td><td> ; . 38 -</td><td> 40°0.</td>

<td> ?;(allyl) Et</td><td> pyrrolidinyl</td><td> solid</td><td> 61 -</td><td> 63°C.</td>

Satisfactory elemental analyses were obtained for all the compounds listed above.

EXAMPLE 3

This Example illustrates the preparation of compounds of formula I .

By reacting, the appropriate carbamoyl chloride with the appropriate 3-sulpha.moyl-l,2,4-triazole in an analogous manner to that described in Example 1“ the follCwing compounds were' prepared.

<td> A':'</td><td> krt</td><td> Phvskal</td><td> ץ5־;י׳.:פ0</td>

<td> N(allyl)₂</td><td>₂&lt;׳</td><td> solid</td><td> . 54 55°C.</td>

<td> L'(allyl)₂</td><td> fflu₂</td><td> solid</td><td> 85 - 84¼</td>

<td> H(allyl)₂ '</td><td> . N(St)Hex</td><td> oil</td><td>⁵?״Ί.5052 jj</td>

<td> t;(allyl)₂</td><td> N(Bu)Pr</td><td> oil</td><td> ’1.505 ²³_(;מ</td>

<td> i(allyl)₂</td><td> 2,6-dimethyliBorp’iiolinc</td><td> solid</td><td> 87 - 88.5°C.</td>

<td> M(allyl)₂</td><td> N(Me)Bu</td><td> oil</td><td> 1.509 ²⁵מ</td>

<td> M(cycli&gt;hexyl)Me</td><td> N(ife)Bu</td><td> solid</td><td> 109 11 ־c°c.</td>

<td> ״(allyl)Bt</td><td> B(fe)Bu</td><td> solid</td><td> 57/ 53¼</td>

<td> s(allyl)?r .</td><td> N(Me)Bu</td><td> oil</td><td> ¾²⁵ 1.501</td>

<td></td><td> N(cyclohexyl)Ke</td><td> solid</td><td> 68- 69.5°C.</td>

<td></td><td> N(cyclohexyl)M8</td><td> solid</td><td> 74 - 75°0.</td>

<td>^δ*2</td><td> N(Me)3-Bu</td><td> solid</td><td> 47 - 50°C.</td>

<td> !J(allyl)₂</td><td> N(Ke)s-Bu</td><td> oil</td><td> n_D²⁵ 1.5008</td>

<td> K(allyl)₂</td><td> N(allyl)fe ' '</td><td> oil</td><td> n/⁵1.519</td>

<td> .!ט זג 2“‘</td><td> N(allyl)Me</td><td> solid</td><td> 58 - SO°C.</td>

<td> H(cyclohoxyl)”e</td><td> N(allyl)Ke</td><td> solid</td><td> 72 74°C.</td>

<td> li(allyl)&amp;t</td><td> N(allyl)Ke</td><td> oil</td><td> ¾¾515</td>

<td> X(allyl)Pr</td><td> li(allyl)!׳!e</td><td> oil</td><td> n/⁵1.5H</td>

<td> ^allyl)₂</td><td> Φ-Kt’nylallyl),)</td><td> solid</td><td> 66 - 67°C,</td>

<td> !l(allyl)₂</td><td> L. N(4-fluorophenyl)Me</td><td> solid</td><td> 56 - 57°C.</td>

<td></td><td> N(Hluomhenyl)Me</td><td> solid</td><td> 85 - 86°C.</td>

»Fit 2

13t₂l־l(allyl)₂N(r!e)Bu

N(allyl)Et

N(>!t)3u iKEiOBu

K(3t)Bu

N(3־t)Bu li(CE_?C_;־CH)Pr

U(CT₂CECH)rr i:(ch₂chch)?t N(Et)Bu ’;(allyl)cyclohexyl :;(C'i₂0ii₂Cl)?r i;(i.11y])₂allyl) ₂

K(4-chlorophe1yl)Ke

N(4-chlorophenyl)Me

N(Me)Bu

K(Pr)i-Pr

N(Me)Bu ffit₂K(allyl)Me fflt₂i!(allyl)₂N(Me)Bu.

N(allyl)Me

N(He)Bu

N(allyl)₂

Et₂ jrat₂

NBt₂

S(CH₂CBCH)?r

N(CH₂CH₂OSt)₂

<td> Physical state</td><td> Constant 1</td>

<td> solid</td><td> 82 - 85°C.</td>

<td> solid -</td><td> 88.5 - 89.5°C.</td>

<td> solid</td><td> 52 - 55.5°C.</td>

<td> solid</td><td> 51 - 52⁰¢.</td>

<td> oil</td><td> n_D²⁰ 1.496</td>

<td> solid </td><td> 74 - 75°¢. :</td>

<td> oil</td><td> n_D^?0 1.504 /</td>

<td> solid</td><td> 56 - 57.5⁰¢.</td>

<td> oil</td><td> il²⁰ 1.5065</td>

<td> oil</td><td> 1.495</td>

<td> oil</td><td> n_D²⁰ 1.5175 (98.6)</td>

<td> oil</td><td> rijj²⁰ 1.5065 (97.3)</td>

<td> solid</td><td> 33 - 34⁰¢.</td>

<td> solid</td><td> 56 - 57.5⁰¢.</td>

<td> solid</td><td> 71 - 72°C.</td>

<td> solid</td><td> 40 - 42°C.</td>

<td> solid</td><td> 54 - 55°C.</td>

<td> oil</td><td> Dj²⁰ 1.521 (97.3)</td>

i!Uliyl)₂

M(c7clopropyl)&amp;t .

;!(allyl)Hex ;!(allyl)!־?!’

N(all.yl)i-Pr '

1; (allyl) i-Pr };(2-raylallyl)₂ ri(allyl)nex' :(allyl)Hex

-ל׳דז u₂״.

ji(5-chloro?entyl)3t

<img file="IL47995A_D0005.tif" />

¢8¾⁴ teisl ־־state !!(Hex)Pr ׳ . . oil .

ffie₂ solid ®₂ . . ' ' solid .

'ffit₂ solid ׳ : SSt₂ . ׳ ־ ' solid

H(l-ie)Uu ' ' solid

S(allyl)₂solid

H(allyl)Me '. oil

18t₂' oil

N(allyl)₂ , 'oil

H(Bu)Ke. oil !!(Hex)Pr ’ 'solid iffit₂ . . . . . oil !!(CB.CH.OPt)״ ' ' solid

G C £

NEt? ־ solid

H(allyl) oil.

HPr₂ solid

I'(2-chloroallyl)Pr . oil

H(C:!₂CIi₂OKe)Pr'oil

H(allyl)Hex oil ״(cyclopropyl)Et 'solid !i(Cr’₂CH₂03u)allyloil η^θ 1,526 (96,6)

- 37°C.

- 62°C,

- 43°C.

- 70°C. ' 35-38°׳C. . .

' 32 - 35°C. ן י ¾²⁰1.515 יי׳ n_D²⁰ 1.5096 (99.8) n_D²⁰ 1.5075 (94.9) ¾²⁰ 1.497 (95.9) 59 - 60°C.

¾²⁰ 1.506 (88.1) 44 - 45°C.

- 54°C.

' n_D²⁰ 1.5185 '׳ ' no°c.

n_D²⁵ 1.5200 (98.5) nD²⁵ 1.5080 (99.9) nD²³ 1.5078 (98.5) 68 - 70°C.

n_D²⁴ 1.5073 (97.8)

<img file="IL47995A_D0006.tif" />

Physical ׳ Constant . I state

N(allyl)l’r

8(allyl)₂ ' i!(allyl)₂

ρ.Ο

N(2-allyloxye1;hyl)Et.

N(i^־ie)s-Bu

H(He)?en

B(2-chloroallyl)Pr

K(I4e)s-Bu ’';(2,3“dichloroallyl)E־t

ΝΕΐ₂ ®₂ י . .

N(allyl)₂ י m₂ .

K(aiiyi),

<td> oil .</td><td> . n²⁴ 1.5157</td>

<td> solid</td><td> D 0 42 -'44°C.</td>

<td> solid</td><td> 29 - 51°C;'</td>

<td> solid</td><td> 42 45° ־C.</td>

<td> oil</td><td> ¾²⁴ 1.4945</td>

<td> solid '</td><td> 25V</td>

<td> solid.</td><td> 54 55°׳־C.</td>

<td> solid</td><td> 49 - 50 V</td>

<td> solid</td><td> 2¢ - 27°C.</td>

<td> solid '</td><td> 80 - 81°0.</td>

<td> solid</td><td> 45 - 46°C.</td>

(94.7) (99.0)

<td> ii(5u)!-ie</td><td> ' bi(allyl)₂</td><td> oil oil</td><td> η., 1.5005 . n_D^ZU 1.5115</td><td> .(98.5) (98.2)</td>

<td> N(?Jlyl)i-Bu’</td><td> ׳ י</td><td> ' solid</td><td> 59 - 40 V</td><td></td>

<td> N(allyl).Bu , . ־</td><td> N(allyl)₂</td><td> oil</td><td> n_D²⁰ 1.510</td><td> (95.0)</td>

<td> ?:(allyl)i-Bu</td><td> ’’ N(allyl)₂</td><td> oil ' ־</td><td> n²⁰ 1.509 J</td><td> (98.8)</td>

<td> !;(Bt)i-Bu</td><td> ii(allyl)₂</td><td> oil</td><td> 1.505 ²⁰_ע1ו</td><td> (98.4)</td>

<td> ;:(Et)i-Bu</td><td> HBtj</td><td> solid ־</td><td> 55 - 56°C.</td><td></td>

solid' solid

Ii(Me)Pen

N(Bu)Bt

- 49 0.

- 5,2°C.

־2' _:llyl)₂

<td> /) . ^ί&lt;;- ^!i</td><td></td><td colspan="4"> Physical Cnrisiy,¹׳!; stite</td>

<td></td><td> H(Bu)Bt</td><td> solid</td><td> 78 - 79%.</td><td></td><td></td>

<td> 'i(allyl)</td><td> li(allyl)Pr</td><td> oil</td><td>¹¾22 ^1,5158</td><td></td><td></td>

<td> i</td><td> N(allyl)_?</td><td> oil</td><td> n_D²² 1.5028</td><td></td><td> ־-׳ ‘</td>

<td></td><td> Bt₂</td><td> solid ^k</td><td> 78 - 80%.</td><td></td><td> I’,'¹</td>

<td></td><td> N(allyl)Pr</td><td> solid</td><td> 75 77% ־. a ן-</td><td></td><td></td>

<td> s(Bt)i-?en</td><td> N(Bu)Me</td><td> oil</td><td> y 1.4896</td><td> (95.4)</td><td></td>

<td> ’(Ci-’₂C2E)Bt '</td><td> N(allyl)₂</td><td> solid '</td><td> 72 - 74°0.</td><td></td><td></td>

<td> K(C־yHCH)3t</td><td></td><td> solid</td><td> 104 - 106°C. Λ</td><td></td><td></td>

<td> !:(fe)Pan</td><td> Et,</td><td> solid</td><td> 43 - 44 0.</td><td></td><td></td>

<td> ׳׳;Π׳;ο)?ορ.</td><td> N(allyl)₂</td><td> oil</td><td> n₀ 1.504</td><td> ¢98.3) </td><td> 1</td>

<td> X(Bx)Fr</td><td> . N(allyl)₂</td><td> solid</td><td> 38 - 40%.</td><td></td><td> ro n</td>

<td> H(allyl)?en</td><td> Kt,</td><td> solid</td><td> 40 - 41°C. A /</td><td></td><td> Γ</td>

<td> g(5^CSCE)3t</td><td> H(Bu)’ie</td><td> oil</td><td> 1.5073</td><td> (98.9)</td><td></td>

<td> li(״;t)?en</td><td> li(allyl)₂</td><td> oil</td><td> n_D²⁶ 1.5005</td><td> (98.0)'</td><td></td>

<td> ׳ it'Pan:)'!</td><td> KSt₂</td><td> oil</td><td> 1¢⁶ 1.4929</td><td> (99.3)</td><td></td>

<td> υ(3ΐ)Ρ(?η</td><td> l!(Bu)He</td><td> oil</td><td> n_D²⁵ 1.4908</td><td> (99.2) '</td><td></td>

<td> !'(allyl)Pan</td><td> N(allyl)₂</td><td> oil</td><td> n ²⁰ 1.5065</td><td> (99.7)</td><td></td>

<td> ’:(St)?:</td><td> N(allyl)Hex</td><td> oil</td><td> . n_D²⁰ 1.495</td><td> (99.9)</td><td> i</td>

<td> ׳:(allyl) at</td><td> N(CH_?CH₂OMe)Pr</td><td> solid .</td><td> 40 - 41%,</td><td></td><td> 1 ז</td>

<td> ״?(allyl)::</td><td> N(aliylj?r</td><td> solid</td><td> 35 - 57%.</td><td></td><td> i</td>

<td></td><td> N(allyl)Pr </td><td> oil</td><td> n,,²⁰ 1.498</td><td> ¢99.3)</td><td> i</td>

<td> (allyl)P;</td><td> We₂</td><td> solid</td><td> 68 - 70%.</td><td></td><td></td>

<td> .</td><td> 1 ...1111«</td><td> Physical state ־!*..... e</td><td> Constant 1</td>

<td> }־(allyliPr</td><td></td><td> ' oil</td><td> ח? . Y 1.504 (99.2)</td>

<td></td><td> N(St)Me</td><td> oil</td><td> ¾²⁰,1.495 (99.5)</td>

<td></td><td> N(allyl)Et , </td><td> solid ' </td><td> 58 - 60°C.</td>

<td> Kt, </td><td> N(]it)Pr</td><td> *solid</td><td> 97 - 100°C,</td>

<td> K(allyl)₂</td><td> N(Et)?r .</td><td> solid '</td><td> 44 - 45°C. .</td>

<td> N(Bu)Et</td><td> N(Bt)?r</td><td> solid</td><td> 58 - 59°C.</td>

<td> ’(Λ)Ργ'.</td><td> ׳ m₂ . ;</td><td> solid</td><td> 54 - 55°O. ' / .</td>

<td> S(!׳:e)?r י ’</td><td> N(Bu)Me . ׳</td><td> oil</td><td> 1¾²⁵ 1.5025 '(99.0)</td>

<td> N(״'e)Pr</td><td> N(allyl)₂</td><td> oil</td><td> ¾²⁵1.5160 (98.5)</td>

<td> .’^;it2</td><td> N(Ne)i-Bu</td><td> 'solid</td><td> 84 - 86°C.</td>

<td></td><td> N(Pen)Pr ,</td><td> . solid</td><td> 45 - 44°C.</td>

<td></td><td> K(Pen)?r</td><td> solid</td><td> 72 - 73°C.</td>

<td> . ,;מ!!:</td><td> N(fr)i־Pr </td><td> solid</td><td> 106 - 108°C. </td>

<td> S(allyl)₂.</td><td> ‘ N(i~Bu)Me</td><td> solid</td><td> 6? - 64°C.</td>

<td> N(allyl)Et</td><td> N(4-fluorophenyl)Me</td><td> solid</td><td> 68-71⁰¢. </td>

<td> iI(Bt)?en . </td><td> N(4-fluorophenyl)Me</td><td> oil'</td><td> n/⁷ 1.5225</td>

<td> .7(aliyl)Ke</td><td> N(4-fluorophenyl)Me</td><td> oil</td><td> ¾²⁷ 1.5425 '</td>

<td> «(Bt)s-Bu</td><td> N(4-fluorophenyl)Me</td><td> oil</td><td> 1.5260 ²⁶_ע1־</td>

<td> 5(Hex)Me</td><td> N(4-fluorophenyl)Me</td><td> oil</td><td> 1¾²⁶ 1.5222</td>

<td> u(St)Pr</td><td> N(4-fluorophenyl)Me</td><td> solid</td><td> 80 - 82°0.</td>

<td></td><td> N(Hluorophenyl)Me</td><td> solid</td><td> 48 - 52°C.</td>

®®«»?«מ™ יי׳ *י *''“^^?®’?*^^1^'?”^ . ¹י.^,’’' 'י iMkttu. χ &lt; Λ.«ώ1'״ώήΒ;ί4^4«.

i'(it)i-?r

N(sllyl)i-Bu :, _*(allyl)Pr

S(allyl)₂ ' yr.jj.

^.!^2 i(allyl)₂ ’!Rtj ?!(allylfe .

(allylj’ie l'(allyl)Sj

K(allyl)₂ % ' rlitj J(allyl)₂ r'(:it)s-3u }!(iit)s-Bu

L׳(I-:e)Hex ’i(3t)l-?r ״ ‘,U .Mlb_r ״(allyl);.

- Physical Constant

<td></td><td> state ... 1111«</td><td> 1</td>

<td> SMe₂</td><td> solid</td><td> 71 74° ־C.</td>

<td> ffiCp</td><td> oil -te</td><td> 1^²⁰. 1.504 (99.5)</td>

<td> li(Bu)K</td><td> oil</td><td> ' n/° 1.497 (99.7)</td>

<td> N(CH₂CH₂OMe)Bt</td><td> . solid</td><td> 52 - 55°C.</td>

<td> i:(C«₂CH₂OMe)Et</td><td> solid</td><td> 74 - 76°C.</td>

<td> !!(tta)fe</td><td> oil</td><td> η_η²⁵ 1.5070 (99,1)</td>

<td> il(Hex)Me</td><td> solid</td><td> 65 - 64°C.</td>

<td> N&lt;allyl)₂</td><td> oil</td><td> ¾²⁷1.5192 (93,8)</td>

<td> κ₂</td><td> solid</td><td> 59 61° ־C.</td>

<td> S(Bu)Me</td><td> oil</td><td> ¾²⁷ 1.5055 (99,9)</td>

<td> N3u₂</td><td> solid</td><td> 90 - 91°0.</td>

<td> N(Et)Pen</td><td> solid</td><td> 58 - 59°C.</td>

<td> K(Et)Pen</td><td> solid</td><td> '86 - 87°C.</td>

<td> H(2-1wthylallyl)₂</td><td> solid</td><td> 84 - 85°C.</td>

<td> !!(allyl)Bt</td><td> oil</td><td> 99 ' V 1.5192- (99.9)</td>

<td> K{allyi)₂</td><td> ‘ oil</td><td>¹׳Of ¾1.5045 (96,4)</td>

<td> ®₂</td><td> oil</td><td> ¾²⁶ 1.4952 (94.6)</td>

<td> Ii(Bu)Me</td><td> oil '</td><td> n/4.8?) - 1.4928 ״)</td>

<td> K(Bu)Me,</td><td> oil '</td><td> ¾.²⁷ 1.4912 (99.5)</td>

<td> E(3u)3t</td><td> solid</td><td> 59 - 41°C.</td>

<td></td><td> solid</td><td> 61 - 62°0.</td>

<td> li(£t)Me .</td><td>^oil</td><td> ¾²⁰ 1.515 (99.9)</td>

I

ת! ף׳ 1

B(allyl)Pr .

’;(cyclohexyl)fle ־ ־. '( allyl) i-Bu 1;(Ke)?r ' (allyl)₂ • f!(allyl)₂ '

NE־t₂

י. r^2 ) i(Ht)Bu • i(CH₂C3H)?r ' 1!U11y1)₂

N(allyl)₂

N(Et)i-?K1 ;:(Cn_?C=CH)Et

I;(Et)Pen i;(allyl)Ke

<td> !It 11*</td><td> Physical ^R־^te</td><td> Constant</td>

<td> N(4-fluorophenyl)Me</td><td> solid</td><td> 76 77° ״C.</td>

<td> N(4-fluorophenyl)Me</td><td> solid</td><td> 87 - 89°C. .</td>

<td> N(Mluorophenyl)Me</td><td> solid ' </td><td> . 117 - 118°C. HA</td>

<td> N(4-fluorophenyl)fe</td><td> * oil</td><td> (99-7 ) 1.550 ,ף!</td>

<td> N(4-11uorophenyl)Ne</td><td> solid</td><td> 71 - 72.5°C.</td>

<td> N(4-fluorophenyl)Ne</td><td> solid</td><td> 75 - 76°C.</td>

<td> N(4-fluorophenyl)Et</td><td> solid</td><td> 121-125°cJ .</td>

<td> N(4-chlorophenyl)Bt</td><td> solid</td><td> 61 65°C.</td>

<td> N(4־chlorophenyl)Et</td><td> solid</td><td> 99 - 101°C.</td>

<td> 2,6-diraethylnorpholino</td><td> solid</td><td> '. ו ',116-120°C</td>

<td> piperidino</td><td> oil</td><td>ⁿ/° 1.512 ״</td>

<td> piperidino</td><td> oil</td><td>¹ . 1.5275 °/ת</td>

<td> hexaethyleneimino</td><td> solid</td><td> 40 - 41°C. '</td>

<td> 4-raeth,ylpiperidino</td><td> solid</td><td> 64 - 65°C. A</td>

<td> heptamethyleneiinino</td><td> solid</td><td> 54-55 C.</td>

<td> pyrrolidinyl</td><td> solid</td><td> 85 - 84°C. nr</td>

<td> piperidino</td><td> oil</td><td> η»’ 1.4896 (96.5)</td>

<td> piperidino</td><td> solid</td><td> 92 - 9Λ. Λ/'</td>

<td> piperidino</td><td> oil ׳</td><td> (¢98.9 1.5078 ,ת</td>

<td> piperidino</td><td> ' oil</td><td>_Ββ²⁷ 1.5266 (99.6)</td>

<td> piperidino</td><td> oil</td><td> 1.5086 (95.5) !</td>

<td> ,.י»«-!-. . ׳ ¹ '</td><td></td><td> ... ״ ’</td><td> ------_T ...</td><td></td>

<td></td><td></td><td></td><td> «</td><td></td>

<td> i. Λ , L</td><td> !a¥</td><td> Physical</td><td> Constant</td><td></td>

<td> י</td><td></td><td> state</td><td></td><td></td>

<td> N(Hex)?-ie</td><td> piperidine</td><td> oil</td><td> ' n_D²⁶ 1.5070</td><td> (97.8) '</td>

<td> M(Me)Pr י '</td><td> piperidine</td><td> solid</td><td> 91 - 92.5°O.</td><td></td>

<td> N(2-chloroallyl)Pr</td><td> ' ^st₂</td><td> solid</td><td> 50°C.,</td><td></td>

<td> V(2־chloroallyl)Pr</td><td> »(allyl)Me</td><td> oil</td><td> n_fl²⁰ 1.5216</td><td> (98.9)</td>

<td> li(2 _t3-dichloroallyl)Et</td><td> N3t₂</td><td> oil</td><td> n ²⁰ 1.5282 1)</td><td> (98.6)</td>

<td> :'i(2-ehloroallyl)Pr</td><td> N{Me)Bu ’</td><td> oil</td><td> / ו ²⁰ » . n^ 1*&gt;12</td><td> J</td>

<td> N(2-chloroal.lyl)E-t</td><td> N(allyl)₂ '</td><td> solid</td><td> 63 - 64°C;</td><td> /</td>

<td> ?;(2״chloroallyl)Et</td><td> NBt₂ . </td><td> solid</td><td> 87 - 88°C.</td><td> 1</td>

<td> N(2״chl'oroallyl)allyl</td><td> H3t₂ .</td><td> solid</td><td> 57 - 58°C.</td><td> r . rq</td>

<td> ”(2־chloroallyl)allyl</td><td> ffle₂</td><td> oil</td><td> 1¾²⁰ 1.527</td><td> (97.9) '</td>

<td> K(2-ohloroallyl)?r ׳</td><td> N(allyl)₂</td><td> oil</td><td> 20 nf 1.5250</td><td></td>

<td> h(2-chlorcallyl)Bt</td><td> N(4-fluorophenyl)Me</td><td> . oil</td><td> ¾²⁰ 1.547-</td><td> (94.9)</td>

Satisfactory, elemental analyses were obtained for all the compounds listed above.

ii¹

EXAMPLE 4.

This Example illustrates the preparation of compounds ' * \ of formula I .

A solution of 0.03 mole 3־diallylsulphamoyl-l,2,45 triazole,' 8 ml. triethylamine and 0.03 mole of N-ethylN-2-methoxyethylcarbamoyl chloride in 40 ml. of dry tetrahydrofuran was held at room temperature for 3 days. The amine hydrochloride was filtered off and the solvent removed by evaporation. 100 ml, of petroleum ether were added to the mixture and petroleum ether decanted from the liquid layer, formed. This was then dissolved in ’ ether, filtered and the solvent removed by evaporation on the steam bath. The liquid product, 1-LN-ethyl-N(2-methoxyethyl)carbamoyl]-3-diallylsulphamoyl-l,2,4-.

triazole was heated at 100°C. in vacuo for 3 hours at a pressure of lower than 0.2 mm. in order to remove all traces of carbamoyl chloride. The compound which was an oily liquid had a refractive i'ndex nj^ 1.5100,' Assay by GLC showed that 96.15־ of 1-isonier was present. Elemental analysis was satisfactory. ,

The 3-diallylsulphamoyl-l,2,4-triazole intermediate used. in the above preoaration was prepared as in Example -1.

The pren,oration of the carbamoyl chloride reactant \ ' was as follows.

N-ethyl-N-^-methoxyethylamine, b.p, 115 - 116°C, was first prepared by reaction of 3 molecular proportions 5 of.ethylamine with 1 molecular proportion of l-bromo-2methoxyethane. in aqueous solution containing 1 equivalent of sodium hydroxide at 30 - 50°C.

To a stirred solution of 89.1 g. phosgene in 500 ml. dry ether at -20°C. was added a solution of 30.9 g.

N-ethyl-N-2-methoxyethylamine in 50 ml. dry ether, whilst the temperature of the reaction mixture was maintained at -20°C. The stirred mixture was then allowed to warm to room temperature during 1 hour. The reaction mixture was filtered and the filtrate evaporated in vacuo below 25°C.

to remove the solvent and give the product, N-(2methoxyethyl)-!N-ethylcarbamoyl chloride as a nale yellow' liquid. ..

The following comnounds were prepared in a. similar manner.

״ .39 -

<td></td><td></td><td> Physical state יי fc—</td><td> Constant '.</td>

<td> N(2“0Hyl0xyethyl)Et</td><td> c.</td><td> oil</td><td> . ¾²² 1.5055 (?8.4) '</td>

<td> E((S₂/₂׳S’e)Pr</td><td> . 148¾</td><td> oil</td><td> 22 (97.5) 1.4982¾ ־</td>

<td> N(OH₂CH₂O?e)Et</td><td> • N(allyl)₂ .</td><td> oil</td><td> n/³ 1.5100 (96.7) '</td>

<td> ίίCH₂CH₂OKe)Et</td><td> ־ Kt₂</td><td> oil</td><td> . n ²³ 1.5005 (96.8) 1</td>

<td> n(s₂ch₂®₂0mK</td><td> 118¾ </td><td> oil</td><td> ¾²² 1.4965 (97.8)</td>

<td> 7¾¾()¾)¾</td><td> N(allyl)₂</td><td> oil</td><td> 2? Pj 1.5061' (96.:) !</td>

<td> ri(CE₂C־i״)?r</td><td> m₂</td><td> solid</td><td> 57.5 . 58.5°C. 0</td>

<td> 70Η/Ε₂0:.»)?γ</td><td> N(allyl)₂ '</td><td> oil</td><td> no w p1 (95.9) 1-5025 ״</td>

<td> .K{CH*CH₂GVe)h?</td><td> . N(?u)fle</td><td> oil</td><td> 2fi ' n_D 1.4914 (96.0)</td>

<td></td><td> piperidino</td><td> solid</td><td> 75.5 - 75.5°C.</td>

<td> n(CH₂CH₂®!e)Pr '.</td><td> li(i־iluoropcenyl)lie</td><td> oil</td><td> p1.5224 ²⁸״</td>

<td> N(CH₂CH₂CBt)P1&gt;</td><td> NHt₂</td><td> oil</td><td> p &gt; »_D²⁵ 1.4925 (97.1) .</td>

<td> n(CH₂CH₂OBt)Pr</td><td> N(Bu)Me</td><td> oil ,</td><td> Pj²³1.4900 ( 97.1),.</td>

<td> +Mp.-׳. yMu pv Ip Λ.ρ '.111 \1) 1j\i.׳ \ '־</td><td> ' ' H(allyl)₂</td><td> oil</td><td> n_B²³ 1.5026 ' (98.1)</td>

<td> Ti(CH₂CH₂03*)3t</td><td> NEt₂</td><td> oil</td><td> n/³ 1.4950, (98/)</td>

<td></td><td> N(Bu)Me</td><td> oil</td><td> p/³ 1.4910 (97.8)</td>

<td></td><td> ptaidino</td><td> solid</td><td> 77.5° - 75.5 יC.</td>

<td> '־f.'''¹ '*.'^,)T.'! r-1 י ^J » 1ז-</td><td colspan="3"> ,.־η:lyses v/c-re ootained *or all tho coxounds listed above״</td>

<td></td><td></td><td></td><td></td>

?ΓΙΑ 8 י'Ί1 i.; 5 ‘י »-«I » .. —

Thin Examole illustraten th? preparation of a compound of formula I by an alternative method through a triazOle carbamoyl chloride intermediate.

Λ solution of 10.8 3-pineridinosulphonyl-l,2,4-triazole and 7 ml. triethylamine in 100 ml. dry tetrahydrofuran was added dropwise'with stirring to a solution 0-f 5 g. phosgene in 100 ml. dry tetrahydrofuran, the temperature being maintained below 15°C. during the addition by ice/water cooling

Precipitation occurred immediately and the mixture was stirred for a further 30 minutes on completion of the addition. The precipitated triethylamine hydrochloride was then'filtered off.

A solution of 6 g. N-propyl-N-2-methoxyethylamine in

50 ml. dry tetrahydrofuran together with 7 ml. triethylamine was added dropwise with stirring and cooling to the filtrate prepared above, the temperature being maintained below 20°C. There was an immediate precipitate and the mixture was stirred for a further 30 minutes on completion of the addition.

The precipitated triethylamine hydrochloride was filtered off and the solvent removed from the filtrate by vacuum distillation. The residue was dissolved in methylene chloride and washed, successively, with50 ־ ml. ^2 sodium hydroxide solution, with 50 ml. water and finally with 50 ml. ¹¹^2 hydrochloric acid. The residue was dissolved in methylene N / chloride and then washed with three 75 ml, portions of 2 sodium hydroxide solution to remove the׳triazole by-product, with 75 ml. water, and finally with 75 ml. ^2 hydrochloric acid. The solvent was removed to give?a solid product which after two recrystallizations from benzene/40 - 60°C. petrol rd :.:tin•0 gave the pure product, 1 -[?:-propyl-:’-(2-me th ox ycthyl) .

carhcrny? ]-^,»-pi)'oridinor.ulp:T.onyl-l,2_>4־־triazolo, m.p. 74 - 7?.5 ^λ׳

EXAMPLE $ '

This Exr;;7jr,lc: illustrates the preparation of a compound \ ' * 5 ־ \ of formuia. I by on alternative method through a carbonylbistriazole intermediate.

A solution of 21.6 g. 3-piperidinosulphonyl-l, 2,4-triazolo and 14 ml. triethylamine in 100 ml. dry tetrahydrofuran was added dropwise with stirring to a solution of 5g. phosgene 10 in 100 ml; dry tetrahydrofuran, the temperature being kept below 15°C. during the addition by. ice/water cooling. Precipitation occurred immediately and the mixture was stirred for a further JO minutes on completion of the addition. The precipitated triethylamine hydrochloride was then filtered off.

A solution of 5.85 g. N-propyl-M-2-methoxyethylamine in .50 ml. dry tetrahydrofuran was added dropwise with stirring to the filtrate prepared above. An exothermic reactiontook place and the reaction mixture was cooled to maintain the temperature bslov/ 20°0. The mixture was stirred for 30 .

minutes on completion of the addition.

The solvent was then removed from the mixture by vacuum distHlotion to give a solid product m.p. 71°0 - 63־, After crystallization from benzene/40-60°0, petrol mixture the pure product was isolated, l-[N-propyl-N-(2-m.ethoxyethyl)car״ . 25 bamoyl]-3-piperidinosulphonyl-l,2,4-triaf5ole; m.p. 72 - 74°0.

״ 42:;:AMPLE 7..

Tills 1.0נףי.ה>:צ illustrates compositions comprising a compound of formula T .

\ . λ disnproibls nowrtcr was prepared by grinding together s '' a mixture of tho-following ingi'edients in a hammer mill* l15״iallylcarbamoyl3״(l-piperidylsulphonyl)-l,2,4-triazole25.0

Sodium N-mcthyl~N-palmitoyltaurate6-0

Sodium di-octylsulphosuccinate .0.5

Colloidal silicic acid ‘25.0

Kaolin43.5

Similar dispersible powders were prepared using the following active ingredients in place of the triazole compound in the above formulation.

l-diallylcarbamoyl-3-dipropylsulphamo.yl-l, 2,4-triazole 1-diallylcarbamoyl-3-pyrrolidinosulphonylrl,2,4-triazole l-diethylcarbamoyl3־׳-diallylsulphan1oyl-l,2,4-triazole l-diallylcarbamoyl-3-diethylsulphamoy1-1,2,4-triazole l-(N-allyl-N-ethylcarbamoyl)-3-(l-piperidylsulphpnyl)-

1,2,4-triazole l-(TI~methyl-N-cyclohexylcarbamoyl)-3-diethylsulphamoyl-

1,2,4-triazole l-(N-methyl-Ll-cyclohexylcarbamoyl)-3-diallylsulphamoyl25 1,2,4-triazole l-diallylcarbamoyl-3-(l'-piperidylsulphonyl)-1,2,4-triazole ' 1

I ״ ’ י ־ י Λ

I

I r\ * 4 ** .״־ז ־

I —ν'ΓΙ.Η _θ ׳ ׳ | This Example Illustrates compositions, comprising

״ . '0 h \ . . . .

I \ a compound of formula I .

? An emulsifiable concentrate suitable for dilution ., k with water ־to form an aqueous emulsion Was prepared from

[ the following ingredients.

L ׳ ’ . ׳ ^w/v

H l-Diallylcarbamoyl-3-(N-allyl-Wmethylsulphamoyl)-l,2,4-triazole20.0

L0 Calcium dodecylbenzenesulphohate2.5 i Nonylphenoxypolyethoxyethanol* . ².5.

! Xylene

Ϊ. . .

* Λ. nonylphcnol-ethylene oxide condensate containing :ן an average of 14׳mols. ethylene oxide per mol. nonylphenol.

1׳ . ..

A similar emulsifiable concentrate was prepared in ΐ which the triazole compound in the above formulation was

. ח >i replaced by the following compound.

g . l-(N-allyl-N-propylcarbamoyl)-3-diethylsulphamoyl~ ' 1,2,4-triazole.

Ί '׳ יי * .

Jo EXAMPLE .9 . ' .'.׳.

This Example illustrates the use of compositions comprising a compound of formu]a II, i In tests carried out in the glasshouse, trays of ij soil were sown with seeds of various weeds and then

J '.

' - 44 -׳ .

'ו-

-.' ־ י ו-

. . ;.;לי,i immediately sprayed with aqeuous suspensions of compounds under test at various application rates of test compound. Seeded trays of boil receiving ⁿ0 chemical treatment were used as controls. At an application rate of 0.5 lb./ acre, all.the triazoles mentioned in Examples .17 and 18 controlled the weeds crabgrass, barnyard grass, yellow foxtail and Johnson grass (no germination or emergent seedlings severely and irrecoverably stunted).

EXAMPLE 10 _ ’

This Example illustrates the use of herbicidal compositions comprising a compound of the formula I., Compositions were prepared ~ ״ containing the following compounds as active ingredients: 1-(N-buty1-N-ethylcarbamoyl)-3-(K-allyl-N-methylsulphamoyl)1,2,4-triazole.

1-(N-ethyl-N-methylcarbamoylj-3“Pyrrolidinosulphonyl-1,2,4-triazole i-(N-allyl-N-ethylcarbamoyl)-3*־dially5ulphanioyl-1,2,4-triazole.

־-diethylcarbamoyl-3-diallylsulphamoyl-1,2,4-triazole.

1-(N-allyi-N-propylcarbamoyl)-3*־diethylsulphamoy 1-1,2,4-triazole.

Rice seedlings were grown under paddy conditions in the glasshouse. At the 2-3 leaf stage the trays containing the .׳ ' seedlings were seeded with barnyard grass and then sprayedj ; 15 with aqueous emulsions prepared from the above concentrates,H

J at an application rate of active ingredient of 8 lb./acre.!

׳ י . . ו *Η

I After seven days the trays were flooded with water and: i ־ ^J . .i ;

j examined 21 days after, spraying.! j

I Jip barnyard grass was observed in the trays sprayedI !

j 20 with the aqueous emulsions described above, and no lasting ί phytotoxic effect on the rice plants was observed. AL.

i growth of barnyard grass had occurred in control trays that!

i had received no chemical treatment.