CA1041096A - 1-dimethylcarbamyl-3-branched alkyl-1,2,4-triazol-5-yl-(n-substituted) sulfonamides and use as insecticides - Google Patents

Abstract

Abstract of the Disclosure Triazolylsulfonamides of a limited class are substantially non-phytotoxic and are useful as insecti-cides. For example 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide is effective in aphid control, both by foliar application and systemically.

Description

:
~ DESCRIPTION OF THE INVENTION
' It is known that some carbamyltriazolylsulfon-amides are useful as herbicides. However, we have dis-. covered that substantially non-phytotoxic compounds - which are extraordinarily effective as both systemic and .
;.: contact insecticides are members of the class having the . generic structural formula .
`''' . `'' ' :
',:', ' ~ 2 ,............................................. / .: ~
. R4 O=C-N
\ N~ R3 ~ :

; R5 ~, '` ~. . :::

. ':;. ,~
,: ~ ` '.: ' , .. .. .
. :

. ` , .. , ~
.. " `,.-: .
: -2- ~ :
- :
. ' .

, . - , , ~ .

104~0~
in which R is C3 to C4 secondary or tertiary alkyl or cycloalkyl, R is hydrogen or methyl, R3 is methyl, R4 is hydrogen, methyl or ethyl, R5 is methyl or ethyl or ;: R4 and R5 together may be a20, with the added provision ;~,k 5 that when Rl is tert.butyl, R4 may also be C3 or C4 alkyl or cycloalkyl, R may also be C3 or C4 alkyl or ; cycloalkyl or phenyl or R and R5 together may also re-, present the remainder of a 3- to 6- membered ring structure, as for example, one of the following:
.

/CH2-CH2 lCH3 / CH2CH2 -' lS) ~ CH-fH2 ~CH2 . CH2-CH2 , ~CH-CH ~C C/

."A. CH3 .~ .
'''' ' : ~ ` f ~C~CH2 The nature of the substituent group Rl appears to be particularly critical with respect to absence of phyto-toxicity and efficacy as insecticides. The nature of the substituents, R and R5 also has an observable effect on insecticidal characteristics, both on contact and . . .
systemically.

Preferred compounds are those which are effective : both systemically and by contact, as they are more versatile and more economical to use to combat chewing or sucking . .
.
_3_ S-553 .' , .
. .
.

` 104109~
insects such as aphids. Particularly preferred compounds are those in which Rl is te~ t . bu~yl. A laboratory method -~ of preparation of these compounds from cor~ercially avail-js ` able intermediates is as follows: -Preparation of 3-tert . butyl-4H-- 1,2,4-triazolin-5-thione ';
To a suspension of 50 g (0.55 mol) of thiosemi-carbazide and 43 g (0.05 mol) of pyridine in 300 ml of dioxane was added 42.6 g (0.6 mol) of pivalyl chloride, with cooling. The reaction was stirred at room tempera-ture for 72 hours, then poured into water. The resulting ~
solid was collected, washed with water and dried. The ~-unpurified pivalyl thiosemicarbazide was heated at reflux temperature in 300 ml of 10~ sodium hydroxide solution for 3 hours. After cooling, the pH was adjusted to 4 with hydrochloric acid and the product collected, washed with :- -water and dried to give 43.8 gr m.p. 200-203. Recrystalli-zation from methanol chloroform gave a sample, m.p. 203-205.
Using a similar procedure, 3-isopropyl-4H~1,2,4-triazolin-5-thione, m.p. 194-5, was prepared.
The structural formula may be written in either the thiol or thione form, as shown in the outline of synthesis reactions below.
.~;.. ; . . , -: , .:
', ,; - ~ .
;: , , .. '~v .- :
~ -4- S-553 ,''' .'~
,:; :

, .
.. : . ', ' .

'" la4l0~6 Synthesis o~ 3-tert.butyl-4H-1,2,4-triazol-5-yl N,N-dimethylsulfonamide .~ This synthesis may be conveniently accomplished . ~ , . .
~ by means of two steps which are outlined as follows:
., .

1.)HS ~ ~Cl ~ ClSO2 ~ N
~ H C(CH3)3 E li c (CH3~3 . ,~' . .
., , , . ' .

2.) ClSO2 ~ +(CH3)2NH ~(CH3 ) 2N-S~ 11 H-N C(CH3)3 H-~- ( 3)3 Reaction 1.) " ' ' ' ' ; Chlorine gas is introduced through a fritted glass delivery tube beneath the surface of a stirred slurry of 50 g (0.32 mol) of 3-tert.butyl-4H-1,2,4-triazolin-5-thione in . 450 ml water. The temperature of the reaction mixture is maintainea at 0 to -10 by means of an ice-salt bath. When absorption of the chlorine is complete (about 76 g C12) the slurry is filtered and the solid washed with water. When dry, the solid 3-tert.butyl-4H-1,2,4~triazol-5-yl sulfonyl chloride melts at 166-168. The solid is used while still slightly damp for the next step in the reaction sequence.

:.

. ' ' ' ' ~

`;` 104~

.:.. : : .
;~ Reaction 2.) ,, ~ .
, ;~ .
:'" The entire product from reaction 1.) is added ~,~, in small portions to 72 g (0.64 mol) of 40~i aqueous di- ~
' methylamine wi~h stirring and cooling. The slurry is ~-stirred one hour, then the solid is filtered and washed with water to give 46.0 g (62% yield) of 3-tert.butyl-,~ 4H-1,2,4-triazol-5-yl N,N-dimethylsulfonamide, . .
m.p. 204-207.
, By using similar procedures and various commer-cially available amines in Reaction 2.) a great variety . . .
;'~ of compounds ha~ing structure II may be prepared.
; ~.. . .
::':'.~,' . :-, .
. "i . ': ~ ' ' N-SO2 ~1 ~N II
.' R H-N ll Rl Specific examples of such compounds are listed below:

R R -~- - R5 m p. (C) rJ 15 (CH312CH- CH3 CH3 162-4 ;~1 (CH3)3C- C2H5 C2H5 158-60 ;~
(CH3)3c- C2H5 H 194-6 ~";,, (CH3)3C- CH3 H 205-7 ' '' (CH ) C H H 166-172 (CH3)3c- -CH2-CH2-0-CH2-CH2- 229-231 : - ,. , .:
.:

.
:, , -6- S-553 ' , : .
' , . ' ., .

~ 1(341096 . .
Synthesis o~ l-N,N-dirnethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfona~lide (Compound No. l)_ ~"~
.
~` - o=f -N(CEI3)2 (CH3)2NS2 ~cl-~-N(cH3)3 --~ (CH3)2NSO ~ N ~N
H- C(CH3)3 N ~ C(CH3)3 ~. ~
Dimethylcarbamyl chloride (3.4 g, 0.032 mol) is added 510wly to a solution of 4.2 g (0.018 mol) of 3-tert.butyl-4H-- 1,2,4-triazol-5-yl N,N-dimethyl sulfonamide in 20 ml of benzene and 20 ml of ~yridine. After refluxing overnight, the mixture is evaporated and the residue is partitioned between water and .
10 chloroform. The chloroform solution is evaporated and the . .
residue parti;ioned between water and ether. Evaporation of the ether solution and recrystallization of the residue from hexane gives l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-..-. !
5-yl-N,N-dimethylsulfonamide (compound No. 1) m.p. 108-110.
~, . .
Synthesis of l-N-methylcarbamyl-. 3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide ''.
' ,:.:~
0=IC-NHCH3 (CH3)2NSO ~ ~ ~CH3-NCO ~(CH3)2NSO ~
- H-N C(CH3)3 ( 3)3 -:.
~ .
A solution of 8.0 g (0.034 mols) of 3-tert.butyl-~ 4H-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide and 3.4 g ~. . ~ . : ;; -. , .

` lV~1096 (0.06 mol) of methyl isocyanate in 20 ml of triethylamine is stirred overnight at room ternperature. The solvent is ; evaporated under vacuum and the residue is slurried in water. The resultant solid is collected by filtration and recrystallized from ethanol to give l-N-methylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide, m.p. 193-194.5.
Using procedures of the type exemplified above, the following compounds represented by structural formula I

,;' ,. ' / R

R \ ~ N \ \ R3 N 1I Rl '. ' :
,. . . .
were prepared, as listed below.
..,;

.' ' :
' ~ ' . .

- -.' .. . ~ ,. . .
. : . .

''''' 104~0~
COMPOUND MELTING POINT (Dey. C.) l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethyl- 93-95 sulfonamide 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(3-oxapenta-methylene~sulfonamide dec. 183-185 l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfon- 90-92 - l-N,N-dimethylcarbam~1-3-tert.butyl-1,2,4-triazol-5-yl-sulfonamidesemi-solid ~ l-N,N-dimethylcarbamyl-3-tert.butyl-; 1,2,4-triazol-5-yl-N-methylsulfon-162-165 amide l-N-methylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide 56-60 l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-pentamethylene- 106-108 sulfonamide .
l-N,N-dimethyl-3-propyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide semi-solid l-N,N-dimethylcarbamyl-3-tert.butyl-: ~ 1,2,4-triazol-5-yl-N-butyl-N-methyl-semi-solid -~ 25 sulfonamide : l-N,N-dimethylcarbamyl-3-isopropyl-.. : 1,2,4-triazol-5-yl-N,N-die-thyl- oil sulfonamide - l-N,N-dimethylcarbamyl-3-tert.butyl-. 30 1,2,4-triazol-5-yl-N,N-(1,4-~imethyl- oil ; tetramethylene)sulfonamide l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-propylsulfonamide oil l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(l-oxa-4,4-dimethyltetramethylene)sulfonamide oil l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-phenylsulfonamide oil '' ', .

-; 104~Q9~i .
~ COMPOUND MELTING POINT (Deg. c.) .::
l-N,N-dimethylcarbamyl-3-cyclo-propyl-1,2,4-triazol-5-yl-N,N- 92-95 dimethylsulfonamide 1-N,N-dimethylcarbamyl-3-cyclo-propyl-1,2,4-triazol-5-yl- oil N-ethylsulfonamide l-N,N-dimethylcarbamyl-3-cyclo-propyl-1,2,4-triazol-5-yl-sulfonylazide 63-67 .
.,? l-N,N-dimethylcarbamyl-3-teYt.butyl-- 1,2,4-triazol-5-yl-N-benzyl-N-iso-propylsulfonamide 126-127 l-N,N-dimethylcarbamyl-3-tert.butyl-. ~ 15 1,2,4-triazol-5-yl-sulfonyl azide oil :.'. .
':
,.'~.~ ' ' `~

.~ -:
. , ~ ~ . .: .: . :
, , :
. .
', , ' ' "
.

: .
. : .
.

. . , : ' ' , " ' . .; ' .' .~ '; , ' :
- :
: ,.

104~0~
The structure illustra~ed by st~uctural formula I
above corresponds to the chemical names assigned to the compounds listed above and is considered most li~ely correct for these compounds. The presence of two other ` 5 possible isomeric structures represented by structural formulas III and IV cannot, however, be excluded.
". -'.

~4 N
\NSO2 ~ N R \ N \ ~ R2 R~ ll 1 R~ ~N/------ i Rl R

R~ O l .;:., III IV

.......
~,i INSECTICIDAL USE
:,, -----The insecticides listed above were employed in the -~; 10 killing of insects according to the following procedure, so as to obtain comparative data:
Two 5 oz. Dixie cups containing Henderson Dwarf lima bean plants and one 5 oz. Dixie cup containing Orange Gem nasturtiums, all growing in vermiculite, are placed on the turntable, and sprayed to thorough wetness with 25 ml of an aqueous dispersion of the candidate chemical at con-centrations of 500, 250, 125, 62, 31 and 15 ppm. Nasturtiums were already infested with 50-100 bean aphids. The effects on aphids were judged by examination of the nasturtium plants 24 hours later and were rated according to the following schedule:

' ~ S-553 : , .

:

.

0 = none dead 1 = 1-25 percent dead , ..
; ; 2 = 26-50 percent dead - .:
` 3 = 51-75 percent dead 4 = 76-99~ percent dead .;. ~ . ~
5 = 100 percent dead ,: . , , ~: ~ All of the compounds listed above gave a rating of 5 at concentrations of 500, 250 and 125 parts per ; million. All but seven also gave a rating of 5 at 62 parts lX;;~
;~ 10 per million concentration. All but si~ of the compounds on , the list gave a rating of at least 4 at only 15 parts per ;~ million, indicating that they were capable of giving satis-.
`~; factory control with repeated spraying at this concentration ~' level. The following compounds gave a rating of 5 (total kill), even at the lowest concentration ~15 ppm) and are preferred aphicides on the basis of contact efficacy.
,' ' . ' ' l-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethyl- -sulfonamide. ~ -1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfon-amide.
: l-N,M-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-sulfonamide. -- 25 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-methylsulfon-amide.

l-N-methylcarbamyl-3-tert.butyl-1,2,4-- triazol-5-yl-N,N-diethylsulfonamide.

' :
: . .
:,~. . . .

~)410~
... , . i . ` .
l-N,N-dimethylcarbamyl-3-te~t.butyl-~- 1,2,4-triazol-5-yl-N,N-pentamethylene-sulfonamide.
:.
1-N,N-dimethylcarbamyl-3-tert.butyl-~ 1,2,4-triazol-5-yl-N~butyl-N-methyl-;; sulfonamide.
:, .J
l-N,N-dimethylcarbamyl-3-tert.butyl-- 1,2,4-triazol-5-yl-N-propylsulfonamide.
~" ,, When 20 ml of aqueous dispersions of l-N,N-- i dimethylcarbamyl-3-ter~.butyl-1,2,4-triazol-5-yl-N,N-~`l dimethylsulfonamide was applied at various concentrations to the soil in which plants were growing instead of the . . . .
; foliage, systemic aphicidal activity was demonstrated.
.~,.......................................................... . .
~`' This is shown in the table below, in which the same ` 15 scoring system was used and Meta Systox R was included -~!
` in the same experiment as a standard for comparison , ........................................................... . .
:
Score of Test Score of Concentration (p~m) Compound Meta Systox R

....
The aqueous dispersions employed in the above , ~ illustrative examples were prepared by dissolving 25 mg.
of aphicidal compound in 5 ml. of acetone and then diluting to the desired concentration with water contain-ing 1.2 ml. of a commercial octylphenoxy polyethoxyethanol non-ionic surfactant (Triton X-100) per liter. By keeping surfactant concentration constant during dilution, dis-.
persion is quick and the resulting homogeneous liquid has : 3C the appearance and behavior of a true solution. By - spraying at a variety of concentrations, the efficacy * Trade Mark .'',- ,~ ..' ' ~' .

-, ", .

~;
:
::: lV41~9~

of the aphicides is demonstrated and a standard is provided , -~ by means of which the skilled worker in the art can adjust the concentration to suit his needs. Water-dispersible solutions of the aphicides are readily prepared by conven-,x;~ 5 tional methods, employing non-phytotoxic commercially ~ -~
available emulsifiers, dispersing agents and auxiliary ~i .. . .
~, solvents. Other additives may be employed in formulations to reduce spray drift and aerosol formation, regulate ., .
, viscosity and for other purposes, according to known practices.
In commercial use the aphicides are conveniently stored and shipped in the form of water-dispersible solutions i ~i or wettable powders and are diluted with water just prior to spraying. Because of the rather high efficacy of the compounds it is impractical to apply them uniformly to plants without ~,..................................................................... . . .
~ 15 some sort of carrier or diluent. Water is the preferred ~' , .
carrier or diluent but either or both solid and liquid diluents ~' may be employed with the aphicides of this invention. The - aphicides may be conveniently formulated as liquid emulsifia~le concentrates or as emulsifiable powders according to repre-: . :
~ 20 sentative procedures given below. All parts are parts by -~

;` weight unless otherwise indicated.
:: -" Wettable Powder Aphicide , 10 parts ~' Barden clay 8 parts , 25 Sodium dialkylnaphthalene 1 part sulfonate (75~ active;
;~ *Sellogen HR) - Sodium-based lignin sulfon- 1 part ate dispersing agent : 30 *(Polyfon H) , , * Trade Marks :
.
.
, :' ' . ! . . ' . ~ ,, ~ ' . . ... ' ':

; :

:; ~
1~4109f~
i.`. ~
;~ The resulting dry powder was easily dispersed , in water to make up liquids for spray application.

' Water Dispersible Concentrate , In a solvent mixture containing 257 parts of ...
:', 5 isophorone and 257 parts of mesityl oxide there was . .:;, , dissolved 40 parts of aphicidal compound, 30 parts of i#i lipophilic emulsifier blend of anionic and nonionic surfactants (T-Mulz 0) and 30 parts of a hydrophilic emulsifier blend of anionic and nonionic surfactants (T-Mulz W). The resulting liquid was a 6.5 percent active water-emulsifiable concentrate which was useful f~)r rep~ring Aqueotl~ ~sprav mixtllres.
. . .
The aphicides of this invention may also be formulated according to conventional methods as oil , 15 sprays, microencapsulated powders, dusts and thickened ; aqueous sprays. The aphicides of the present invention need not be applied directly to the body of each insect, but only to the locus of the insects, that is, the place inhabited by the aphids, generally stPms and foliage.
~ 20 Whether the aphids contact the aphicide during or after ,,- spraying is immaterial. Toxicity of the compounds to other types of insects, in general is relatively low, so that . .~ .
populations of predatory and competing species will remain established, even though plants are sprayed to obtain a substantially complete kill of aphids.
~ ., * Trade Marks i: . '.
'"' ' :
.

.
' S~s ~' .

Claims (40)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide.

2. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(3-oxapentamethylene)sulfonamide.

3. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide.

4. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-sulfonamide.

5. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-methylsulfonamide.

6. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N-methylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide.

7. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-pentamethylenesulfonamide.

8. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethyl-3-propyl-1,2,4-triazol-5-yl-N,N-dimethyl-sulfonamide.

9. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-butyl-N-methylsulfonamide.

10. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-isopropyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide.

11. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(1,4-dimethyltetramethylene)sulfonamide.

12. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-propylsulfonamide.

13. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(1-oxa-4,4-dimethyltetramethylene)sulfonamide.

14. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-phenylsulfonamide.

15. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide.

16. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-N-ethylsulfonamide.

17. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-sulfonylazide.

18. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-benzyl-N-isopropylsulfonamide.

19. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-sulfonyl azide.

20. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide.

21. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(3-oxapentamethylene)sulfonamide.

22. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethysulfonamide.

23. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-sulfonamide.

24. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-methylsulfonamide.

25. 1-N-methylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide.

26. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-pentamethylenesulfonamide.

27. 1-N,N-dimethyl-3-propyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide.

28. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-butyl-N-methylsulfonamide.

29. 1-N,N-dimethylcarbamyl-3-isopropyl-1,2,4-triazol-5-yl-N,N-diethylsulfonamide.

30. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(1,4-dimethyltetramethylene) sulfonamide.

31. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-propylsulfonamide.

32. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N,N-(1-oxa-4,4-dimethyltetramethylene) sulfonamide.

33. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-phenylsulfonamide.

34. 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-N,N-dimethylsulfonamide.

35. 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-N-ethylsulfonamide.

36. 1-N,N-dimethylcarbamyl-3-cyclopropyl-1,2,4-triazol-5-yl-sulfonylazide.

37. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-N-benzyl-N-isopropylsulfonamide.

38. 1-N,N-dimethylcarbamyl-3-tert.butyl-1,2,4-triazol-5-yl-sulfonyl azide.

39. The method of killing aphids on plants comprising applying to the plants a substantially non-phytotoxic but aphicidally effective amount of a compound having the generic structural formula I

in which R1 is C3 to C4 secondary or tertiary alkyl or cycloalkyl, R2 is hydrogen or methyl, R3 is methyl, R4 is hydrogen, methyl or ethyl, R5 is methyl or ethyl or R4 and R5 together may be azo, with the added provision that when R1 is tert.butyl, R4 may also be C3 or C4 alkyl or cycloalkyl, R5 may also be C3 or C4 alkyl or cycloalkyl or phenyl or R4 and R5 together may also re-present the remainder of a 3- to 6- membered ring structure, selected from one of the following:

, , ,

40. A compound having the generic structural formula I

in which R1 is C3 to C4 secondary or tertiary alkyl or cycloalkyl, R2 is hydrogen or methyl, R3 is methyl, R4 is hydrogen, methyl or ethyl, R5 is methyl or ethyl or R4 and R5 together may be azo, with the added provision that when R1 is tert.butyl, R4 may also be C3 or C4 alkyl or cycloalkyl, R5 may also be C3 or C4 alkyl or cycloalkyo or phenyl or R4 and R5 together may also re-present the remainder of a 3- to 6- membered ring structure, selected from one of the following:

, , ,