Hydrocarbylthioalkanethiols

Claim 2

A composition according to claim 1, 6-(t-butylthio)-1-hexanethiol.

Claim 3

A composition according to claim 1, 8-(t-butylthio)-1-octanethiol.

Claim 4

A composition according to claim 1,8-(t-butylthio)- 1-octanethiol.

Claim 5

A composition according to claims 1 wherein R is alkyl and R'' is hydrogen.

Claim 6

A composition according to claim 1, wherein R is alkyl and R'' is hydroGen. The extract was distilled under reduced pressure yielding 31.3 g. (89 mol percent based on the amount of 8-(t-butylthio)-1-octyl methanecarbothiolate charged) of a fraction boiling at 110* C./0.22 mm. Hg, having a refractive index at 20* C. of 1.4911 and a density at 20* C. of 0.9219. Elemental composition calculated for 8-(t-butylthio)-1-octanethiol is 61.5 percent carbon, 11.2 percent hydrogen, and 27.4 percent sulfur. Elemental composition found by analysis for the product was 61.5 percent carbon, 11.3 percent hydrogen, and 27.5 percent sulfur. These values are in excellent agreement with the theoretical and thus confirm the structure of the compound as named. This example clearly demonstrates another preparation of the hydrocarbylthioalkanethiols of the invention by the reaction of a hydrocarbylthioalkyl hydrocarboncarbothiolate with a base. EXAMPLE V In order to demonstrate the utility of the thiol compounds of the invention, a butadiene/styrene copolymer was prepared in an emulsion-type recipe employing the 8-(t-butylthio)-1-octanethiol prepared in Example IV as the modifier. A control run was made using the same recipe employing tert-dodecylmercaptan (Sulfole 120) as a modifier. The polymerization recipe was as follows: Polymerization Recipe Parts by weight 1,3-Butadiene 70 Styrene 30 Water 180 Dresinate 554 (a) 4.6 KOH 0.125 KC1 0.30 Daxad (b) 0.20 Questex 4SW (c) 0.032 FeSo4.7H2O 0.010 NaSO2CH2OH.2H20 0.050 p-Menthane hydroperoxide 0.063 Modifier (d) variable Shortstop: Thiostop N (e) 0.16 Antioxidant: Polygard (f) 1.5 Temperature, * F. 41 Time, hours variable (a) Potassium salt of a disproportionated rosin acid, (b) Sodium salt of polymerized alkyl napthalenesulfonic acid. (c) The tetrahydrate of the tetrasodium salt of ethylenediamine tetraacetic acid. One-half added in soap solution (KOH, KC1, Daxad 15 and Dresinate 554 in water) and one-half in activator solution (FeSO4.7H20 and NaSO2CH2OH.2H10 in water). (d) Sulfole 120 tert-dodecyl mercaptan. (CH3)3CS(CH2)8SH (e) Sodium dimethyldithiocarbomate. (f) Tri(nonylphenyl)phosphite. Charge Order: soap solution, styrene, butadiene, modifier (see below for details of incremental addition of (CH3)3CS(CH2)8SH. All of the tert-dodecyl mercaptan was added at this point), p-menthane hydroperoxide, adjust temperature to 41* F. for 25 minutes, activator solution. TABLE I Run No. Modifier Time I.V. Mooney No. (phm) (a) Hours % (b) ML-4(c) (CH3)3CS(CH2)8SH 7.0 59 44 (0.299) (d) 2 tert-C12SH 7.1 61 2.05 52 (0.186) (a) Phm parts by weight per 100 parts by weight of monomers. (b) Determined according to the procedure of U.S. 3,278,508, column 20, notes a and b. Polymers were gel-free. (c) ASTM D 1646-63. (d) 0.0748 phm added at 0, 15, 33 and 49 percent conversion. The above polymers were isolated by first adding antioxidant to the shortstopped reactions, then coagulating with salt/acid at a pH of 3 to 4. Recovered polymers were washed once at room temperature, then three times at 50- 60* C. and dried overnight at 155* F. in an air oven. The above polymers were compunded in a conventional rubber recipe. The compounding recipe and results are shown below. Compounding Recipe Parts by weight Polymer 100 IRB No. 2 Carbon black (a) 50 Philrich 5 (b) 10 Zinc oxide 3 Stearic acid 1 Flexamine G (c) 1 Sulfur Sulfur 1.75 Santocure (d) 1.2 (a) Industry reference black, high abrasion furnace type. (b) Highly aromatic oil, type 101 under ASTM D 2226-63T. (c) A mixture containing 65 percent of a complex diarylamine-ketone reaction product and 35 percent of N,N''-diphenyl-p-phenylenediamine. (d) N-cyclohexyl-2-benzothiozolesulfenamide. TABLE II Processing Properties Polymer from Run No. 1 Run No. 2 Compound Mooney, ML-4 (a) 54 58 Extrusion - 250* F., (b) Garvey inches/min. 44 42 g./min. 113 110 Rating (Garvey, 12 best) 11 11-L Physical Properties (Cured 30 min. at 307* F.) 300* Modulus, p.s.i. (c) 1,170 1,100 Tensile, p.s.i. (c) 3,710 4,040 Elongation, p.s.i. (c) 665 680 Delta T, * F. (d 83.5 77.2 Resilience, Percent (e) 59.2 62.4 Shore A Hardness (f) 58 58 (a) ASTM D 1646-63 (b) Ind. Eng. Chem., 34, 1309 (1942) (c) ASTM D 412-62T (d) ASTM D 623-62 (d) ASTM D 945-59(f) ASTM D 1706-61 This example clearly demonstrates the utility of the hydrocarbylthioalkanethiols as modifiers in a polymerization system. EXAMPLE VI To demonstrate the utility of the hydrocarbylthioalkyl hydrocarboncarbothiolates of the invention, the 8-(t-butylthio)-1- -octyl methancarbothiolate produced in Example III was tested for its insecticidal effectiveness on the Mexican Bean Beetle (Epilachna varivestis). In the Mexican Bean Beetle spray test, the effectiveness of the 8- (t-butylthio)-1- octyl methanecarbothiolate as applied to one-day old larvae of the beetle was accomplished as follows. Paired fully expanded primary leaves were excised from Pinto bean plants. The leaves were sprayed with 50 ml. of a formulation which had the following recipe: