Structure of Dipropyl disulfide
CAS No.: 629-19-6
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Synthesis of N-Sulfenylimines from Disulfides and Primary Methanamines
Robert Kawȩcki ;
Abstract: N-Sulfenylimines (sulfenimines, thiooximes, N-alkylidenesulfenamides) were efficiently synthesized through the reaction of primary amines and disulfides with NBS or bromine. This reaction can be carried out in an open flask at room temperature without the need for any transition-metal-containing additives. The use of thiols instead of disulfides gave similar results. A wide range of amines were reacted with aryl and alkyldisulfides, resulting in the formation of sulfenimines in a yield of 44–99%.
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| CAS No. : | 629-19-6 |
| Formula : | C6H14S2 |
| M.W : | 150.31 |
| SMILES Code : | CCCSSCCC |
| English Name : | 1,2-Dipropyldisulfane |
| MDL No. : | MFCD00009378 |
| InChI Key : | ALVPFGSHPUPROW-UHFFFAOYSA-N |
| Pubchem ID : | 12377 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sulfur at 130℃; unter Zusatz von Dibutylamin; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 32.6% 2: 2% 3: 55.1% | With boron trifluoride diethyl etherate; sulfur dioxide In dichloromethane at 25℃; for 24h; | |
| 1: 55.1% 2: 32.6% 3: 2% | With boron trifluoride diethyl etherate; sulfur dioxide In dichloromethane at 25℃; for 24h; other thiols, var. time, var. amount of BF3OEt2; | |
| 1: 55.1% 2: 32.6% 3: 2% | With boron trifluoride diethyl etherate; sulfur dioxide In dichloromethane at 25℃; for 24h; |
| With 5-chloro-3H-benzo[c][1,2]dithiol-3-one In [D3]acetonitrile; water-d2 at 25℃; for 0.25h; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 70 % Chromat. | With bis(triphenylstannyl)tellurium In acetonitrile for 72h; Ambient temperature; | |
| With copper In N,N-dimethyl-formamide at 40℃; for 12h; Glovebox; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 71% | With boron tribromide; potassium iodide In 1,2-dichloro-ethane at 80℃; for 16h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 1.5 % Chromat. 2: 13.0 % Chromat. 3: 77.0 % Chromat. | With sodium hydroxide; hydrazine hydrate In water at 50 - 70℃; for 0.5h; | |
| With sodium sulfide; tetrabutylammomium bromide; sulfur In water at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 15% 2: 29% | With triethylamine In dichloromethane at 25℃; for 2h; Further byproducts given; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 22% 2: 48% 3: 30 % Chromat. | With polysulfide; tetraethylammonium perchlorate In N,N-dimethyl-formamide in situ electrochemical generation of polysulfide from carbon-sulfur cathode; Title compound not separated from byproducts; | |
| 1: 22 % Chromat. 2: 30 % Chromat. 3: 48 % Chromat. | With polysulfide; tetraethylammonium perchlorate In N,N-dimethyl-formamide in situ electrochemical generation of polysulfide from a carbon-sulfur cathode; Title compound not separated from byproducts; | |
| 1: 30 % Chromat. 2: 48 % Chromat. 3: 22 % Chromat. | With polysulfide; tetraethylammonium perchlorate In N,N-dimethyl-formamide in situ electrochemical generation of polysulfide from carbon-sulfur cathode; Title compound not separated from byproducts; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With potassium hydroxide; hydrogen sulfide In dimethyl sulfoxide at 30℃; for 5h; Title compound not separated from byproducts; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 96% | With dinitrogen tetraoxide; pyrographite In dichloromethane at 20℃; for 0.25h; | |
| 94% | With 1H-imidazole; manganese(II) tetraphenylporphyrinate; tetra-n-butylammonium hydrogen monopersulfate In dichloromethane at 20℃; for 0.0166667h; | |
| 80% | With 1,1,1,3',3',3'-hexafluoro-propanol; water; lithium perchlorate; acetic acid at 20℃; for 8h; Electrochemical reaction; chemoselective reaction; |
| Multi-step reaction with 2 steps 1: 77 percent / MCPBA / CH2Cl2 / 0.25 h / 0 °C 2: 8 percent Spectr. / MCPBA / CDCl3 / -40 deg C, 17 min -> -20 deg C | ||
| With Hg; dihydrogen peroxide In acetic acid | 4.A (A) (A) n-Propyl n-propanethiosulfonate n-Propyl disulfide (37.575 g, 0.25 mole) was dissolved in 90 ml of glacial acetic acid in a 500 ml three-neck flask fitted with a reflux condenser and 100 ml dropping funnel. The reaction flask was first cooled to 0° C., and with vigorous stirring, a solution of 56.7 g (0.5 mole) of hydrogen peroxide (30%) was added slowly through the dropping funnel while maintaining the temperature below 10° C. Initially the reaction mixture existed as two layers. After addition of hydrogen peroxide, the solution was stirred for 30 minutes at 0° C. and the flask was then slowly warmed to 60° C. over the course of one hour, while it gradually became a homogeneous solution. [Slow warming of the flask was necessary; otherwise the reaction becomes extremely exothermic.] After a test for peroxide became negative (KI-starch paper), the glacial acetic acid was removed in vacuo at 45° C. The oil was diluted with 150 ml of saturated NaHCO3 solution and extracted throughly with chloroform. The chloroform solution was dried over anhydrous Na2 SO4 and evaporated in vacuo to give an oil. Distillation under 2.0 mm of Hg gave 29.1 g of the title compound, boiling point 110°-115° C. | |
| 44.a a) a) 1-Propyl1-propanethiolsulfonate In the same manner as in Preparation 38-a), 666 mg of 1-propyl 1-propanethiolsulfonate was obtained from 1.57 ml of dipropyl disulfide. NMR(CDCl3): 1.04 (3H, t, J=7.4 Hz), 1.09 (3H, t, J=7.4 Hz), 1.7-1.85 (2H, m), 1.9-2.05 (2H, m), 3.05-3.15 (2H, m), 3.25-3.35 (2H, m) |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 71% | Stage #1: 3-(trifluoromethyl)anisole With n-butyllithium; N,N,N,N,-tetramethylethylenediamine; diisopropylamine In tetrahydrofuran; hexane at -70 - 0℃; Inert atmosphere; Stage #2: Dipropyl disulfide In tetrahydrofuran; hexane at -70 - 20℃; | |
| With n-butyllithium In tetrahydrofuran; hexane | 1 1. 1. Preparation of 2-Propylthio-3-(trifluoromethyl)-anisole A solution of 30 mL (milliliter) (208 mmol) (millimole) of 3-(trifluoromethyl)anisole in 500 mL of dry tetrahydrofuran was cooled to -70° C. under a nitrogen blanket and 100 mL (250 mmol) of 2.5M butyl lithium in hexane was added slowly with stirring and cooling. The reddish solution was stirred at -70° C. for 1 hour and then 42 mL (270 mmol) of dipropyl disulfide was added slowly with stirring and cooling. The resulting mixture was allowed to warm to ambient temperature over an 18-hour period. The mixture was quenched with 250 mL of saturated aqueous ammonium chloride. The organic phase was recovered, dried over magnesium sulfate, and concentrated by evaporation under reduced pressure. The yellow oil residue was fractionally distilled in a Vigreux column at 0.2 mm Hg (millimeters of mercury) (27 Pascals) to obtain 37 g (gram) (71 percent of theory) of a clear liquid product fraction boiling at 92° C. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 36% | To a chilled(-78 C) solution of 1-chloro-6-fluoro isoquinoline (59mg, 0.32 mmol) in 2 mL of THF was added LDA solution in cyclohexane (1.5 Molar, 0.23 mL, 0.35 mmol). The orange solution was stirred for 2 hrs before it was treated with n-propyl disulfide (60ZL, neat material, excess). The reaction was allowed to warm to room temperature over 30 min. It was quenched with a solution of half saturatedNH4CI, the organic residues were extracted into ethyl acetate. LC-MS analysis indicated about50% conversion into the desired product along with mainly starting material. The desired product was purified by a short column (4 cm X 2 cm, silica gel type-H) eluted with 5% ether in hexanes, 29mg (36% yield) of the desired product was obtained. LC/MSRt-min(MH+) [method C] : 3.79(256).'H NMR (400 MHz, CHLOROFORM-D)8 ppm 0.96 (t, J=7. 34 Hz, 3 H) 1.52 (m, 2 H) 2.86 (m, 2 H) 7.45 (dd, J=9.29, 8.56 Hz,1 H) 8.34 (d,J=0. 73 Hz, 2 H) 8.37 (m,1 H). | |
| The following procedure is equally applicable to other 5-alkylthio-6-alkoxy isoquinolines by changing the reagents shown here. To a solution of 1-chloro-6- fluoro isoquinoline (88mg, 0.48 mmol) in 2.0mL THF under nitrogen at-78 C was added LDA (1.5 Molar in cyclohexane, 0.42 mL, 0.63 mmol) forming a dark brownish solution. Neat n-propyl disulfide(85, uL, excess) was introduced after it was stirred at-78 C for 30 min. The reaction was allowed to warm to room temperature over a period of 30 min. It was quenched with a solution of half saturatedNH4Cl, the organic residues were extracted into ethyl acetate. The organic layers were combined and dried under vacuum to 50 microns (Hg). The crude product was taken into 2 mL of THF, cooledto-78 C, added with excess potassium ethoxide (60mg). The isoquinoline intermediate was finally purified by a silica gel column (type-H, Merck) eluted with ether-hexanes mixture, 32.2mg (24%) of the pure compound was obtained. LC-MS showed 1-chloro-5-propylthio-6-ethoxyl isoquinoline at rt-min(MH+) [method C]: 3.77 (282).'H NMR (400 MHz, CHLOROFORM-D)8 ppm 0.94 (t, J=7. 34 Hz, 3 H)1. 46 (m, 2 H) 1.55 (t, J=6. 97 Hz, 3 H) 2.83 (t, J=7. 21 Hz, 2 H) 4.32 (q,J=6. 85 Hz, 2 H) 7.36 (d,J=9. 29 Hz,1 H) 8.22 (d, J=6. 11 Hz, 1 H) 8.32 (d, J=9. 29 Hz,1 H) 8.35 (d, J=6. 11 Hz,1 H). |
[ 110-81-6 ]
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[ 629-19-6 ]
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[ 72437-63-9 ]
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[ 68794-86-5 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With tricyclohexylphosphine In dimethyl sulfoxide at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 90% | With dihydrogen peroxide; methyltrioxorhenium(VII) In acetonitrile at 20℃; for 0.0166667h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 81% | With copper(l) chloride; isopentyl nitrite; In acetonitrile; at 20 - 60℃; for 2h;Inert atmosphere; | General procedure: Compound 3a or 3b (5.85 mmol) was added into the dry acetonitrile (35 mL) containing appropriate dialkyl(aryl) disulfide (40.95 mmol) and CuCl (0.29 m mol). The mixture was purged thoroughly with N2 and stirred at room temperature for 30 min. Isoamyl nitrite (4.25 g, 36.3 mmol) was added to the solution immediately, the reaction was stirred for 30 min at room temperature, and then the mixture was heated at 60 °C. The reaction time was listed in Table 2. The disappearance of the starting material was monitored by TLC (EtOAc/P.E., 1:10, v/v). After removing CuCl, the solvent and other volatiles were removed under reduced pressure. The residue was purified by column chromatography (Et3N-neutralized silica gel, gradient elution separation with EtOAc/P.E., 1:40-1:20, v/v) to afford the product as colorless or yellow oil. |