US3845092A - 1,3-bis-(substituted-disulfan)-2-alkylamino propanes - Google Patents

Abstract

1. A COMPOUND OF THE FORMULA:

R1-N(-CH(-S-S-C(=S)-O-R3)2)-R2

WHEREIN R1 IS ALKYL OF 1 TO 5 CARBON ATOMS, R2 IS HYDROGEN OR ALKYL OF 1 TO 5 CARBON ATOMS, AND R3 IS ALKYL OF 1 TO 8 CARBON ATOMS OR CYCLOALKYL OF 5 OR 6 CARBON ATOMS, OR AN AGRICULTURALLY ACCEPTABLE ACID ADDITION SALT THEREOF.

Description

United States Patent US. Cl. 260-455 B 18 Claims ABSTRACT OF THE DISCLOSURE The invention concerns novel 1,3 bis-(substituted-disulfan)-2-alkylamino propane compounds of the formula:

R, is alkyl of 1 to carbon atoms, R is hydrogen or alkyl of 1 to 5 carbon atoms and Qis wherein wherein R is alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 or 6 carbon atoms and R is alkyl of 1 to 5 carbon atoms.

The compounds possess insecticidal activity.

This application is a continuation-in-part of our copending application Ser. No. 230,125, filed Feb. 28, 1972, now abandoned.

The invention relates to 1,3-bis-(substituted-disulfan)-2- alkylamino propane derivatives.

The invention provides compounds of formula I,

wherein R is alkyl of l to 5 carbon atoms, R, is hydrogen or alkyl of 1 to 5 carbon atoms and Q is wherein R is alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 or 6 carbon atoms and R is alkyl of 1 to 5 carbon atoms.

When R R R or R are alkyl, these may be straight or branched chained.

The invention also provides a process for the production of a compound of formula I, which comprises reacting a compound of formula II,

R and R are as defined above and Y is a suitable leaving group, e.g. toluene sulphonyl or benzene sulphonyl,

wherein with a compound of formula III,

MQ III wherein Q is as defined above and M is an alkali metal.

The compounds of formula I may exist either in free base or acid addition salt form. Acid addition salt forms may be obtained from free base forms and vice versa in conventional manner.

The process of the invention may be eifected as follows VIZ.

To the compound of formula II dissolved in a suitable solvent e.g. methanol, ethanol or acetonitrile, is added a compound of formula III. The mixture may intially be stirred at room temperature eg for up to three hours. Subsequent heating with stirring to 50 C., e.g. for V2 to 1 hour may be effected.

The reaction mixture is worked up in the usual manner. The compounds of formula I are obtained as oils in free base form thereof, which are soluble in organic solvents. Acid addition salt forms may be obtained from free base forms by salification and may be characterised by melting point.

The compounds of formula II employed as starting material in the production of the compounds of formula I may, for example, be obtained by reacting a compound of formula IV,

wherein R and R are as defined above and X is halogen, preferably chlorine,

with a compound of formula V,

MeSY V wherein Y is as defined above and Me is a suitable metal or ammonium cation, preferably sodium,

in an appropriate solvent, such as methanol, ethanol or isopropyl.

The compounds of formula IV and V are produced in accordance with processes described in the literature.

The compounds of formula I possess insecticidal activity as indicated in each of the following tests.

TEST (i) Insecticidal effect against Bruchidius obtectus (bean weevil)contact elfect Petri dishes having a diameter of 7 cm. are coated by spraying with 0.1 to 0.2 cc. of an emulsion containing 0.0125% of a compound of formula I. After drying the coating for about 4 hours, 10 Bruchidius imagoes are placed in each dish which is covered with a lid comprising a fine mesh brass wire grid. The insects are kept without food at room temperature. After 48 hours the rate of mortality is determined.

TEST (ii) Insecticidal effect against Ephestia kuelmiella (flour moth)--contact effect Petri dishes having a diameter of 6 cm., each containing 10 caterpillars 10 to 12 mm. in length, are coated by spraying with 0.1 to 0.2 cc. of an emulsion containing 0.05% of a compound of formula I. The dishes are then covered with a fine mesh brass wire grid. After drying the coating a Wafer is given as food and renewed as required. After 5 days the rate of mortality is determined by counting the live and dead insects.

TEST (iii) Insecticidal effect against Calandra (Sitophilus) granaria (grain weevil)contact effect Petri dishes having a diameter of cm. are coated on a turn table through three turns under a fixed spraying noz zle, with a liquor of a compound of formula I in a concentration of 500 p.p.m After drying the coating for 4 hours 30 imagoes are placed in the dish. After 1 to 2 days the dead insects are counted.

TEST (iv) Insecticidal effect against Prodenia litura (cotton stainer)contact and feed effect 10 Prodenia larvae are placed in several Petri dishes having a diameter of 10 cm. They are coated by spraying with a liquor containing a compound of formula I in a concentration of 500 p.p.m. Bush beans used as fodder plants are coated to run off with the above liquor by the same method: after drying the coating the larvae in the dishes during the test receive the treated beans as food. Mortality is determined after 6 days.

In addition, the compounds possess low toxicity in warm blooded animals as indicated by LD determinations on male white rats.

The compounds are therefore useful as insecticides particularly in animal buildings e.g. stables, inhabited rooms e.g. cellars and attics, and in plant loci.

For the abovementioned use the amount of the compound to be applied will vary depending on the particular compound employed, the mode of application, ambient conditions and the effect desired. With regard to plant protection, in general a suitable amount to be applied to a plant locus is between 100 g. and 2 kg./hectare.

The compounds may be employed as a composition with insecticidal carriers and diluents in solid or liquid form e.g. spraying nad dusting powders, strewing granulates, sprays ing liquids and aerosols.

Solid forms may include diluents and carriers such as diatomaceous earth, talc, kaolinite, attapulgite, pyrophyllite, artifical mineral fillers based on SiO and silicates, lime, decahydrate and plant material carriers such as walnut and flour. Adjuvants such as wetting and dispersing agents, e.g. sodium-lauryl sulphate, sodium dodecyl ben zenesulphonate, condensation products from naphthalene sulphonate and formaldehyde, polyglycol ether and lignin derivatives such as sulphite liquor, may also be included in the case of wettable powders to be applied as a water suspension. Granulates are produced by coating or impregnating granular carrier materials such as pumice, limestone, attapulgite and koalinite with the compounds.

Liquid forms may include non-phytotoxic diluents and carriers such as alcohols, glycols, glycolic ethers, aliphatic and aromatic hydrocarbons e.g. xylene, alkyl naphthalenes and other petroleum distillates, and ketones e.g. cyclohexanone and isophorone. Adjuvants such as surface active agents, e.g. wetting and emulsifying agents such as polyglycol ether formed by the reaction of an alkylene oxide with high molecular weight alcohols, mercaptans or alkyl phenols, and/or alkyl benzene sulphonates, may be included in emulsion concentrate forms.

Aside from the abovementioned carriers, diluents and adjuvants, adjuvants such as stabilizing agents, deactivators (for solid forms with carriers having an active surface), agents for improving adhesiveness to surfaces treated, anticorrosives, defoaming agents and pigments may also be included.

Concentrate forms of composition generally contain between 1 and 90% preferably between 5 and 50% by weight of active compound.

4 Application forms of compositions generally contain between 0.02 and preferably between 0.1 and 20% by weight of active compound.

Examples of concentrate forms of composition will now be described.

(a) Emulsifiable concentrate: 25 parts by weight of a compound of fromula I are mixed with 25 parts by weight of isooctylphenyldecaglycol ether and 50 parts by weight of xylene, whereby a clear solution is obtained which may be readily emulsified in water. The concentrate may be diluted with water to the desired concentration.

(b) Emulsifiable concentrate: 25 parts by weight of a compound of formula I are mixed with 30 parts by weight of isooctylphenyloctaglycol ether and 45 parts by weight of a petroleum fraction having a B.P. of 210-280" (D 0.92). The concentrate may be diluted with water to the desired concentration.

(c) Emulsifiable concentrate: 50 parts by weight of a compound of formula I are mixed with 2 parts by weight of soidum-lauryl sulphate, 3 parts by weight of sodiumlignin sulfonate and 45 parts by weight of kaolinite. The concentrate may be diluted with water to the desired con centration.

Free base and acid addition salt forms of the compounds of formula I exhibit the same ytpe of activity. Examples of agriculturally acceptable acid addition salt forms are the hydrogen, acetate, hydrogen benzoate, hydrogen oxalate, and hydrogen sulphate.

The preferred compounds of formula I are the following viz.

1,3-bisl-n-butoxythiocarbonyl-disulfan-2 -2-dimethylaminopropane, 1,3bis-(1-isopropoxythiocarbonyl-disulfan-Z)-2-dimethylaminopropane,

1,3-bis-( l-n-pentyloxythiocarbony1-disulfan-2 )-2-dimethyl-aminopropane,

1,3-bis-( 1-sec.butoxythiocarbonyl-disulfan-2) -2-dimethylaminopropane,

and the preferred acid addition salt form thereof is the hydrogen oxalate.

The production of compounds of formula I will now be desicribed in more detail by way of Example. Where temperature is referred to, this is in C.

EXAMPLE 1 1,3-Bisl-n-pentyloxythiocarbonyl-disulfan-2 -2- dimethylaminopropane (free base form) 22.2 g. (0.11 mol) of p0tassium-n-pentylxanthogenate are added by portions at room temperature and while stirring to 21.6 g. (0.05 ml.) of 1,3-bis-(benzenesulphonylthio)-2-dimethylaminopropane in 200 cc. of absolute methanol. After stirring the mixture at room temperature for 3 hours it is heated to 50 C. and stirred for about half an hour. After cooling the mixture to room temperature it is filtered off from the precipitated potassium benzenesulfinate and the solvent is evaporated in a vacuum. The residue is taken up in 300 cc. of chloroform and Washed twice with cc. amounts of water. After drying the chloroform solution with sodium sulphate it is evaporated in a vacuum.

The remaining oil may be set free from the volatile constituents by heating to 50 during the course of half an hour in a high vacuum.

Analysis.C H NO S molecular weight: 475.8. Calc. (percent): C, 43.0; H, 7.0; N, 2.9; S, 40.4. Found (percent): C, 43.2; H, 6.3; N, 3.3; S, 40.2.

In an analogous manner to that described in the foregoing example the following compounds may be produced viz.

1,3-bisl-cyclopentyloxythiocarbonyldisulfan-Z) -2- methyl-n-pentylaminopropane, and

1,3-b1 s-( 1-n-octyloxythiocarbonyl-disulfan-Z) -2-dimethylaminopropane.

EXAMPLE 2 1,3-Bis-( 1-n-pentylo;xythiocarbonyl-disulfan-Z) -2- dimethylaminopropane-hydrogenoxalate 4.0 g. (0.0084 mol) of 1,3-bis-(l-n-pentoxythiocarbonyldisulfan-Z)-2-dimethylaminopropane are dissolved in 30 cc. of absolute ethanol. A solution of 1.0 g. (0.011 mol) of anhydrous oxalic acid in cc. of absolute ethanol is Analysis.C H NO S molecular weight: 419. Calc. (percent): C, 37.2; H, 6.0; N, 3.3; S, 45.9. Found (percent): C, 38.1; H, 5.5; N, 3.6; S, 45.2.

The corresponding hydrogen oxalate is produced in analogous manner to that described in Example 2.

In analogous manner to that described in Examples 1 and 2, the following compounds of formula I and the acid addition salts thereof may be obtained.

Analysis, percent Acid addi- Molec- Calculated Found tion salt Empirical ular M.P.IB.P. Example R1 R: Q form formula weight; (mm. C H N S G H N S OH; SCS-OCzHa. Cu 21 O2Sn 391 86/0.002 33.7 5.4 3.6 49.1 33.6 5.8 4.3 49.6 CH; SOS-00111 Hydlftgtel'l Cl3H23NOBS6-- 481 107 32.4 4.8 2.9 39.9 32.4 4.8 3.3 39.4

oxaae. CH; sCS--0iC3H1 --do 15 27 O6s6... 509 134 35.4 5.3 2.8 37.7 35.6 5.4 2.9 37.6 CH; SCS-OnC4Hn 15 29N 2 5-. 447 40.3 6.5 3.1 42.9 40.3 6.5 3.6 43.2 CH; SOSO-nC4Ho Hydr e u CnHarNOrSc- 537 955 38.0 5.8 2.6 35.8 38.0 5.7 2.7 35.6

0X9. CH SCSOsec.-C4Ho CHHZDNOZSL- 447 40.3 6.5 3.1 42.9 40.2 6.5 3.8 43.0 CH; SCSOsec.-C4Hn-. Hgdrloggm CUHMNOBSG..- 537 115 38.0 5.8 2.6 35.8 37.8 5.5 2.8 35.7

X88 CH; SCS-O-cyclohexyl C19H33NO2S6- 499 45.6 6.6 2.8 38.5 44.5 6.6 2.8 37.8 CH; SCS-Ocyclohexyl- Hydroggn- C21H35NO6S6-- 589 1l8125 42.8 5.9 2.3 32.6 42.7 6.1 2.7 32.5

oxaae.

added thereto. The precipitated hydrogen-oxalate is re- E A L 14 r stallized from absolute 233 gi ig z z g ig a of 1,3-B1s-(l-isobutoxythiocarbonyl-d1sulfan-2)-2- dimethylaminopropane Analysis.-C H NO S molecular weight: 565. Calc. (percent): C, 40.4; H, 6.2; N, 2.5; S, 34.1. Found (percent): C, 39.6; H, 6.2; N, 2.8; S, 33.9.

EXAMPLE 3 1,3-Bis- 1-acetyl-disu1fan-2) -2-dimethylaminopropane (free base form) 11.4 g. (0.1 mol) of potassium thioacetate are added by portions at room temperature and while stirring to 21.6 g. (0.05 mol) of 1,3-bis-(benzene sulfonylthio)-2-dimethylaminopropane in 400 cc. of absolute acetonitrile. The mixture is stirred at 50 for 1 hour and the reaction mixture is allowed to cool down. The precipitated salt is filtered off. The filtrate is evaporated in a vacuum at 50 and then the residue is taken up in 300 cc. of chloroform and washed twice with 100 cc. amounts of water. The chloroform solution is dried with sodium sulphate and evaporated in a vacuum.

The oily residue is distilled in a high vacuum at 8286/ 0.002 mm.

Analysis.C 'H -;NO S molecular weight: 299.5. Calc. (percent): C, 33.7; H, 5.7; N, 3.6; S, 49.1. Found (percent): C, 33.6; H, 5.8; N, 4.3; S, 49.6.

In analogous manner to that described in the foregoing example 1,3-bis-(l-n-pentylcarbonyl disulfan 2) -2-npentylaminopropane may be produced.

EXAMPLE 4 1,3-Bis-( l-isoprop oxythiocarb onyl-disulfan-Z -2-dimethylaminopropane (free base form) 13.9 g. (0.08 mol) of potassium isopropyl xanthogenate are added by portions at room temperature and while stirring to 17 g. (0.37 mol) of 1,3-bis-(p-toluene sulfonylthio)-2-dirnethylaminopropane in 300 cc. of absolute meth anol. After stirring the mixture at room temperature for 3 hours it is heated to 50 C. and stirred for about one further hour. After cooling to room temperature it is filtered off from the precipitated potassium-p-toluenesulfinate and the solvent is evaporated in a vacuum. The residue is taken up in 300 cc. of chloroform and washed twice with 100 cc. amounts of water. After drying the chloroform solution with sodium sulphate evaporation takes place in a vacuum.

The remaining oil may be set free from the volatile constituents by heating to 50 C. during the course of half an hour in a high vacuum.

21.0 g. (0.11 mol) of potassium n isobutoxyxanthogenate are added portion by portion to 21.6 g. (0.05 mol) of 1,3-bis-(phenylsulphonylthio)-2-dimethylamino propane while stirring at room temperature. After stirring has been continued for 3 hours at room temperature, the mixture is heated to and stirred for an additional hour. After cooling to room temperature the potassium benzenesulfinate formed in the reaction is filtered ofi and the solvent is removed in a vacuum. The residue is dissolved in 300 ml. of chloroform and is washed twice with 100 cc. of water each. After drying the chloroform solution with anhydrous sodium sulfate, the solvent is evaporated 011'.

The oily residue is liberated from volatile impurities by treatment for /2 hour at 50 on a high vacuum pump.

Analysis.C H NO S molecular weight: 447.8. Calc. (percent): C, 40.2; H, 6.5; N, 3.1; S, 43.0. Found (percent): C, 40.0; H, 6.7; N, 3.2; S, 42.8.

537.8. Calc. (percent): C, 38.0; H, 5.8; N, 2.6; S, 35.8.

Found (percent): C, 37.8; H, 5.8; N, 2.9; S, 36.1.

EXAMPLE 16 1,3-Bis-( 1-cyclohexyloxythiocarbonyl-disu1fan-2) -2- dimethylaminoproparm-hydrochloride 20 ml. of dry ether saturated with gaseous hydrogen chloride is added to 4 g. (0.008 mol) of 1,3-Bis-(1-cyclohexyloxy-thiocarbonyl-disulfan-Z) 2 dimethylaminopropane in 20 ml. of absolute ether. After the reagent has been added the ether is evaporated off. The residue is kept on the high vacuum pump at 30 for 1 hour. The hydrogen chloride salt is rather hygroscopic.

Analysis.-C H NO S -HCl; molecular weight: 536.5. Calc.: C, 42.6%; H, 6.4%; Cl, 6.6%; N, 2.6%; S, 35.9%. Fgiunyd: C, 42.5%; H, 6.2%; Ci, 6.1%; N, 3.0%; S, 3 .4 o.

In an analogous manner to that described in the foregoing examples 14 to 16, the following compounds may be produced.

Analysis, percent Molec- Melting Calculated Found Empirical ular point Example R R; Q, Salt formula weight; C.) C H N S C H N S 17 CH CH3 SCSOn-hexyl CrnHmNOzSe 503.9 Oil 45.3 7.4 2.8 38.2 45.0 7. 4 3.2 38. 5 18 CH3 CH3 SCSOn-hexy1 Hydrlogen- Cal-IanNOeSe 593. 9 136438 42.5 6.6 2.4 32.5 42.0 5.9 3. 1 31. 5

oxa a e. 19 CH3 CH3 SCSOn-propyl cia zsNozso 419. 7 Oil 37. 2 6 3. 3 45. 8 37. 6 5. 9 3. 4 45. 20. CH: SOS-O-n-propyL- Hydriogm- CuHuNOaSa 509. 7 127 35. 3 5 3 2. 7 37. 7 35. O 5. 0 2. 9 88. 1

oxa a e. 21 CzH5 C211 SCS-Oi-propyl CnHaaNOzSn 475.8 Oil 42. 9 7. 0 2. 9 40. 4 43. 2 7. 4 3. 1 40. 6

Starting materials: The starting compounds of formula II may be produced in accordance with the following Example:

1,3 Bis (benzene sulphonylthio)-2-dimethylaminopropane: 96.3 g. (0.5 mol) of 1-dimethylarnino-2,3-dichloropropane hydrochloride are dissolved in 500 cc. of alcohol and a solution of 11.5 g. (0.5 mol) of sodium in 400 cc. of alcohol is added. After adding 196 g. (1 mol) of sodium benzene thiosulphonate and further 500 cc. of alcohol the mixture is stirred at 80 for 2 hours. The precipitated sodium chloride is removed by suction from the hot solution. The product crystallizes from filtrate in pure form. M.P. 82-83 C.

In analogous manner to that described in the foregoing Example, 1,3-bis-(toluene sulphonylthio) 2 dimethylaminopropane (which is described in the literature) may be produced by reacting 1-dimethylamino-2,3-dichloropropane and sodium-p-toluene sulphonate.

The substance crystallizes from alcohol in colourless leaflets having a M.P. of 1151l6 C.

What is claimed is:

1. A compound of the formula:

ll B1 ss-c-0 R;

R s-s-ga-on.

wherein R is alkyl of 1 to 5 carbon atoms, R is hydrogen or alkyl of 1 to 5 carbon atoms, and R is alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 or 6 carbon atoms, or an agriculturally acceptable acid addition salt thereof.

2. A compound of Claim 1, wherein R is selected from the group consisting of ethyl, n-propyl, i-propyl, n-butyl, sec. butyl, i-butyl, n-pentyl, n-hexyl and cyclohexyl.

3. A compound of Claim 2, wherein R is selected from the group consisting of ethyl, i-propyl, n-butyl, sec-butyl, n-pentyl, and cyclohexyl.

4. A compound of Claim 3, wherein R and R are each methyl.

6. A compound of Claim 5, wherein R and R are each methyl or each ethyl.

7. The compound of Claim 4, which is 1,3-bis( l-n-pentoxythiocarbonyl-disulfan-Z -2-dimethylaminopropane.

8. The compound of Claim 4, which is 1,3-bis( l-isopropoxythiocarbonyl-disulfan-2 -2-dimethylaminopropane.

9. The compound of Claim 4, which is 1,3-bis-(1-ethoxythiocarbonyl-disulfan-2)-2-dimethylaminopropane.

10. The compound of Claim 4, which is 1,3-bis(1-nbutoxythiocarbonyl-disulfan-Z -2-dimethylaminopropane.

11. The compound of Claim 4, which is 1,3-bis-(1-sec.- butoxythiocarbonyl-disulfan-Z -Z-dimethylaminopropane.

12. The compound of Claim 4, which is 1,3-bis-(l-cyclohexyloxythiocarbonyl-disulfan-Z) 2 dimethylaminopropane.

13. The compound of Claim 6, which is 1,3-bis-(1-isobutoxythiocarbonyl-disulfan-Z -2-dimethylarnino.

14. The compound of Claim 6, which is 1,3-bis-(1-nhexyloxythiocarbonyl-disulfan-Z -2-dimethylamino.

15. The compound of Claim 6, which is 1,3-bis-(l-npropoxythiocarbonyl-disulfan-Z)-2-dimethylamino.

16. The compound of Claim 6, which is 1,3-bis-(l-isopropoxythiocarbonyl-disulfan-2 -2-diethylamino.

17. A compound of Claim 1 in hydrogen oxalate form.

18. A compound of Claim 1 in hydrochloride form.

References Cited UNITED sTATEs PATENTS 3,318,936 5/1967 Sakai et a1 260-455B FOREIGN PATENTS 976,729 12/1964 Great Britain 260-455 A LEWIS GOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner r U.S. Cl. X.R.

Claims (1)

1. A COMPOUND OF THE FORMULA: