CA1065345A - 1,3-bis-(tert-butyldithio)-2-dimethylaminopropane - Google Patents

Abstract

Abstract of the Disclosure 1,3-bis-(tertTbutyldithio)-2-dimethlamino-propane in free base and acid addition salt form is useful as an insecticidal and fungicidal agent.

Description

Case 130-3757 .
S3'~s~
1,3-Bis-(Tert-Butyldithio)-2-Dimethylaminopropane The present invention relates to a 2-aminopropane derivative which possesses insecticidal and fungicidal properties.

Accordingly, the present invention provides 1,3-bis-(tert.-butyldithio)-2-dimethylaminopropane, of the formula I, CH3\ CH2-SS-C(CH3)3 N-CH
CH3/ \ CH -SS-C(CH ) in free base or acid addition salt form.
The acid addition salt forms include those with inorganic acids, e.g. hydrochloric, sulphuric and phosphoric acids, and those with organic acids, e.g.
oxalic, benzenesulphonic, toluenesulphonic, methane-sulphonic, acetic and benzoic acids, of which those forms with hydrochloric and oxalic acids are the most preferred.

The present invention further provides a process for the production of the compound of formula I in 130-~757 ~0~;534S
free base or acid addition salt form, which comprises reacting a compound of formula II, 3 \ ~ CH -S-L
N-CH II

o in which L is a group of formula -S-~l, wherein Rl is an alkyl or aryl radical, and m is O or 1, or L is a group -SO3Ml~ wherein Ml is so~ium or potassium, with a compound of formula III, 3)3 2 III

in which M2 is sodium or potassium, in such a proportion that both "L" moieties in the com-pound of formula II are replaced by -S-C(CH3)3 radicals from the compound of formula III.
In the compound of formula II, the alkyl radical signified by Rl is preferably one containing 1 to 3 15. carhon atoms, and preferred examples of the aryl radical signified by Rl are the phenyl and toluyl radicals. Ml 3'~S

and M2 are preferably each, independently, sodium in the compounds of formulae II and III, respectively.
The production of the compound of formula I is preferably effected by adding the compound of formula III, preferably in solution in a suitable solvent, e.g. water, an alcohol such as methanol, ethanol or propanol, a nitriIe such as acetonitrile, a ketone such as acetone, butan-2- one or cyclohexanone, an ether such as dioxan or tetrahydrofuran, or an amide such as dimethyl-formamide, and preferably with stirring, to the compound of formula II in soluticn or suspension in a suitable solvent or diluent, preferably the same medium as that used for the solvent of the compouna of formula III.
The preferred solvents or diluents are water and methanol. When L in formula II is a -SO3Ml group, the addition is effected at a temperature below room temper-ature, preferebly within the range 0-10C. Generally the sddition is effected over a period from 20 minutes to 2 hours, and a further period of time during which the reaction mixture is stirred and kept cool, or, when using a starting material of formula II in which L is a -8-Rl group, warmed, e.g. to 50C, is often required 10~5345 to complete the reaction. Such additional reaction time is generally between 1/2 and 1 1/2 hours.
The compounds of formulae II and III used as starting materials are either kno~m compounds or can be produced by or analogously to known methods.
The free base form of the compound of formula I
can be converted into an acid addition salt form, and vice versa, by conventional techniques.
It has been found that the compound of the present invention, i.e. the compound of formula I in free base or acid addition sait form, exhibits unexpected stabil-ity, e.g. against light, humidity or heat. This is indicated by a virtual lack of tendency to decompose when distilled under high vacuum or when stored or used under conditions in which it would be expected to be affected by the prevailing light, humidity or heat conditions.
Furthermore, the compound of the invention may be produced in good yields and purity, particularly when using a compound of formula II in which L is a -SO3M
group.
The compound of the invention possesses insec-iO653~5 ticidal activity and is therefore indicated for use as an insecticide. By the term "insect" as used in this specification are included not only members of the class Insecta but also members of related classes of animal organisms e.g. Acaridae such as spider mites.
The terms "insecticide", "insecticidal" and the like are to be construed accordingly.
In its use as an insecticide, the compound of the invention displays a contact effect, a systemic effect and/or an effect through inta~e by feeding. Owing to its stability, it exhibits a prolonged effect. As well as for the combat of biting insects, e.g. Lepidoptera and Coleoptera, the compound is notably suitable for combat of sucking insects. The compound, especially in free base form, is particularly effective against Lepidop-tera, e.g. Egyptian cotton stainers (Spodoptera littoralis), flour moths (Anagasta kuehniella), rice stem borers (Chilo suppresalis), as well as Coleoptera, e~g. potato beetles (Leptinotarsa decemlineata), rice and confused flour beetles (Tribolium castaneum and Tribolium confusum), been weevils (Bruchidius obtectus) and corn chafers 130~3757 aria), and r~e1ml~p~era, e.g. cotton bugs (Dysdercus fasciatus). Moreover, it is also effective against Aphids and Diptera.
The compound of the invention also possesses fungicidal activity and is therefore indicated for use as a fungicide, e.g. against Uromyces phaseoli.
In addition, the compound of formula I in free base or agriculturally-acceptable acid addition salt form advantageously exhibitslow mammalian and fish toxicity and phytotoxity. Agriculturally~acceptable acid addition salt forms are defined as those forms having the same low order of manmmalian and fish toxicity and phytotoxic-ity as the free base form.
The compound of the invention in free base or agrIculturally-acceptable acid addition salt form is particu]arly useful in combatting insects in potato and rice cultures.
The compound of the invention in free base or agri-culturally-acceptable acid addition salt form may be applied to insects or fungi in conventional manner, either by direct application of the compound or by application of the compound in association with an insecticide or fungicide carrier, diluent and/or lO~S345 adjuvant as a formulation. For plant protection the compound may be applied, for example, in the form of liquid or powder sprays, dusting powders, granulates, strewing powders, pastes and aerosols.
granulates, strewing powders, pastes and aerosols.
The liquid sprays, which are emulsion concentrates to be diluted with water before use, contain suitable surface--active agents, such as binding and emulsifying agents, e.g. polyglycol ethers produced from addition of alkylene oxides to higher molecular weight alcohols, mercaptans or alkylphenols, and alkyl benzenesulphonates.
The solid formulations, e.g. dusting, strewing and spraying powders, are produced with conventional inert mineral carriers such as diatomaceous earth, talc, kaolinite, attapulgite, pyrophyllite, artifici~l flll~rs based on silica and silicates, limestone, Glauber's salt and plant carrier substances, e.g. powdered plant material, in conventional manner.
In the case of spraying powders (wettable powders) which are suspendable in water, the formulations contain suitable binding and dispersing agents, e.g. sodium lauryl sulphate, sodium dodecyl benzenesulphate, condensation 10~53~5 products of naphthalene sulphonate and formaldehyde, polyglycol ethers and lignin deritTatives such as sulphite lye extract.

Granulates may be produced by coating or impregnation of granular carriers such as pumice, limestone, attapulgite, kaolinite and plant carrier material with the active agent or a solution or other formulation thereof.
In addition to the previously mentioned carrier and surface-active materials, formulations of the compound of the invention may also contain further additives with special purposes e.g. stabilizers, deactivators (for solid formulations on carriers with an active surface), agents for improving the adhesion to plants, corrosion inhibitors, anti-foaming agents and pigments.
~loreover, further insecticides and/or fungicides may be present in the formulations.
In general, the concentrate forms of formulation, which are also provided by the present invention, contain between 1 and 90~ by weight of a compound of the present invention, preferably between 5 and 50~ by weight. The liquors ready for use contain in general between 0.02 and 90~ by weight of active agent, prefer-ably between 0.1 and 20% by weight.

1~i534~
The amount of compound of the invention when used as an ins~cti.cide or fungicide applied to a locus to be treated will naturally depend upon the particular form of the compound of formula I employed, the particular enviro~ellt ,a~,bient conditions and the species of insect or fungus to be combatted. Ho~lever for plant protection satisfactory results are generally obtained when the compound is applied to a plant locus in an amount between 0.5 and 4 kg/hectare, the application being repeated as required.
Examples of the production of suitable formulations of the compounds of the invention are as follows:

~065345 a) Granulate 5 g of 1,3-bis-(tert.butyldithio)-2-dimethyl-aminopropane are dissolved in 5 g of an aromatic solvent preferably with a boiling point within the range of 185-213C. The solution is sprayed onto 90 g of crushed,thoroughly sieved pumice (grain size 0.3 - 1 mm) by a conventional technique.

.. .. ... . .. ..
b) Emulsion Concentrate .
~) 25 parts by weight of 1,3-bis-(tert.butyldithio)-

2-dimethylaminopropane are mixed with 30 parts by weight of iso-octyl phenyl octaglycol ether and 45 parts by weight of a petroleum fraction with a boiling range of 210-280C (D2o:0.92). The concentrate is diluted with water to the desired concentration.

c) Emulsion Concentrate 50 parts by weight of an acid addition salt of 1,3-bis-(tert.butyldithio)-2-dimethylaminopropane are mixed with 2 parts by weight of sodium laury~ sulphate,

3 parts by weight of sodium lignin sulphonate and 45 parts b~ weight of kaolinite. rrhe concentrate can be d.iluted with wa~er to the desired concentration.

The insecticidal and fungicidal activity of the compound of formula Iin freebase Gr acid addition salt form is indicated by the following tests.

- 10 ~

lOf~S34S

Insecticidal Effect a~ainst Bru~hidius obtectus (1 ) _____________________ _________________________ (bean wee~il) - Contact effect _______________________________ Petri dishes of 7 cm diameter are sprayed ~lith O.i to 0.2 ml of an emulsion produced according to formulation example c) containing 0.0125~ of 1,3-bis-(tert.butyl-dithio)-2-dimethylaminopropane. After about 4 hours drying of the coatings 10 Bruchidius imagines are introduced into each dish, which is then covered with a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 48 hours the death rate is noted (percentage). A 100% death rate indicates that all the bean weevils have died and a 0% death rate means that none have died. The result was a 100~ death rate.

(i.i) Ins~cticidal Effect a~alnst Tribotium confusm __~ _._______________ _______~_ _____________ (confused flour beet_e)- Contact effect Petri dishes of 7 cm diameter are sprayed with 0.4 ml of an emulsion produced according to formulation example c) containing 0.0125% of 1,3-bis-(tert.but~l-dithio)-2-dimethylaminopropane. After about 4 hours drying of the coatings 30 Tribolium imagines are intro-duced into each dish, which is then covered with a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 72 hours the death rate is noted ~percentage). A 100~ death rate indicates that all the beetles have died and a 0%

~30-3757 death rate means that none have died. The result was a 100~ death rate.
(iii) Insecticidal E~fect a~ainst Calandra ~ranaria _____________________ _______________ _______ (corn chafer) - Contact effect _________________.____________ Petri dishes of 5.5 cm diameter are sprayed with 0.4 ml of an emulsion produced according to formulation example c) containing 0.0125~ of 1,3-bis-(tert.butyl-dithio)-2-dimethylaminopropane hydrochloride. After about 4 hours drying of the coatings 30 Calandra-Imagines are introduced into each dish, which is then covered with a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 72 hours the death rate is noted (percentage). A 100~ death rate indicates that all the corn chafers have died and a 0~ death rate means that none have died. The result was a 100~ death rate.
(iv) Fun~icidal Effect a~ainst Uromyces ~haseoli (bean rust~ - Systemic effect __________ ____ ______________ Potted bean plants (Phaseolis vulgaris) in the second leaf stage are watered with 70 ml of an emulsion produced according to formulation example c) containing 0.05% of 1,3-bis~tert.butyldithio)-2-dimethylaminopropane hydrogen oxalate such that the green parts of the plants remain untouched. After 24 hours the plants are infected with bean rust spores (Uromyces phaseoli), after which they are maintained for one day at 100~ relative humidity followed by 8 days at 23 (16 hour days). The extent of plant damage is then evaluated, according to the follow-ing scale in respect of the damage preventative effect of the administered compound:
1 = no significant effect (0.5% effect) 3 = weak effect (5-50% effect) 6 = middling to good effect (50-95~ effect) 9 = very good effect (95-100% effect) The compound displayed an effect with a rating of 9 on the above scale.
10 (v) Fun~icidal Effect against Uromyces Ehaseoli -_______________ __________ ____ _________ Contact effect Potted bean plants in the second leaf stage are sprayed twice with an emulsion according to formulation c) which contains 0.0125~ of 1~3-bis-(tert.butyldithio)-2-dimethylaminopropane hydrogen oxalate, while being turned on a revolving table, each plant being sprayed with about 0.7 ml of the emulsion. The plants thereby receive a thin covering of the emulsion which has no tendency to flow away. The sprayed plants are allowed to dry out.
After 24 hours the plants are sprayed with a suspension of Uromyces spores, and then maintained for 1 day at 100% relative humidity followed by 8 days at 23C (16 hour days). The extent of plant damage is then evaluated according to the scale given in the previous example. The compound displayed an effect with a rating of 9 on this scale.

~0~;53g~5 (vi) Acaricidal Effect a~inst Tetranychus telarius (s~ider mite) - Contact effect A formulation produced as described in formulation example c) is diluted with water to the desired concen-tration. Bean plants (Phaseolis vulgaris) are sprayed with this emulsion containing 0.05~ of 1,3-bis-(tert.-butyldithio)-2-dimethylaminopropane hydrochloride until thoroughly wetted. These plants are infected with spider mites in all stages of development in great abundance.
After 2 days a mortality rate in percentage is deter-mined through counting the numbers of living and dead mites. A 100% mortality rate means that all the spider mites have been killed and a 0% rate, that none have been ki]led. The mortality rate was found to be 100%.

The following examples illustrate the production of the compounds of the present invention. Temperatures are in de~rees Centigrade and the melting points are uncorrected.

~ 14 -10~5345 EX~IPL~ 1 lL3-Bis~(tert.-butyldithi~ 2-dimethyl-.._ _ ________________ ______ _________ _ amino~ro~ane "
_____ __ ___ To a solution produced by stirring 24 g (0.6 moles) of sodium hydroxide in 600 ml of water and subsequently cooled to 0-10 are added 211 g (0.6 moles) of monosodium 2-dimethylamino-propane-1,3-bis-thio-sulphonate. To the resulting solution, maintained at 0-10, is added dropwise with stirring an aqueous solution of sodium salt of tert.-butylmercaptan over a period of 30 minutes. The latter solution is produced by dissolving 48 g (1.2 moles) of sodium hydroxide in ~00 ml of water and then adding 108 g (1.2 moles) of tert.-butylmecaptan dropwise within the temperature range 0-10. After the addition of the sodium salt, the mixture is stirred for a further 30 minutes at 0-10.
To the mixture is then added 600 ml of chloroform, after which it is stirred vigorously for a short time.
The chloroform phase is then separated, washed succes-sively with three 200 ml amounts of water, dried with anhydrous sodium sulphate, and evaporated in vacuo at 50. The resulting oil is warmed at 50 over a period of 30 minutes under high vacuum to free it of the more volatile constituents. On cooling, the concentrated oil crystallises to a product with melting point 45. The product distils without decomposition at 140-145/0.1 mm ~0~5345 of mercury pressure. Its Rf value on thin layer chromatography with silica gel and a 9:1 benzene:
ethyl acetate eluant is 0.4.
Analysis 13 29 4 Molecular weight 327.6 Calc'd. : C, 47.7~ , 8.9% ; N, 4.3~; S, 39.1%
Found : 47.8% 9.0% 4.3% 38.5%
The production of acid addition salts of 1,3-bis-(tert.-butyldithio)-2-dimethylaminopropane is exemplified in the following two examples.

EXAMPLE 2 1 3-bis-(tert -butyldithio)-2-dimethyl-_L___________-____ _________________ _ amino~ro~ane hydro~en oxalate To an ethereal solution of the product of Example 1 is added a slight excess of ethereal solution of oxalic acid, whereupon the hydrogen oxalate salt precipitates.
After collection by filtration the salt is washed with a llttle diethyl ether and subsequently dried during 1 hour in vacuo at 30, giving a product with melting poir,t 114-115.
Analysis13 294 2 24 Molecular weight 417.7 Calc'd. :C, 43.1% , H, 7.5% ; N, 3.4% ; S, 30.7%
Found :42.9% 7.5% 3.8% 30.6%

10~53~ 130-3757 EX~MPLE 3 lL3-bis-(tert -butyldithio)-2-di~ethyl-aminoEro~ane hydrochloride To an ethereal solution of hydrogen chloride in slightly excess amount is added an ethereal solution of the product of Example 1, whereupon the hydrochloride salt precipitates. After collection by filtration the salt is washed with a little diethyl ether and subse-quently dried during 1 hour in vacuo at 30, giving a product with a melting point 158.
Analysis C13H29NS4.HCl Molecular weight 364.1 Calc'd. : C, 42,9~ ; H, 8.3%; Cl, 9.7%; N, 3.8%; S, 35.2~
Found : 42.9% 8.4~ 9.9% 3.8% 35.3%

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of formula I, I

in free base or acid addition salt form.

2. An acid addition salt form of a compound according to Claim 1, in which the acid is selected from hydrochloric acid, oxalic acid, benzenesulphonic acid, toluenesulphonic acid, methanesulphonic acid, sulphuric acid, phosphoric acid, acetic acid and benzoic acid.

3. A process of producing a compound according to Claim 1, comprising reacting a compound of formula II, II

in which L is a group of formula , wherein R1 is an alkyl or aryl radical, and m is 0 or 1, or L is a group -SO3M1, wherein M1 is sodium or potassium, with a compound of formula III, (CH3)3CSM2 III

in which M2 is sodium or potassium, in such a proportion that both "L" moieties in the compound of formula II are replaced by -S-C(CH3)3 radicals from the compound of formula III.

4. A method of combatting insects or fungi in a locus which comprises applying to the locus an insec-ticidally- or fungicidally-effective amount of a compound of formula I, as defined in Claim 1, in free base or agriculturally-acceptable acid addition salt form.