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Please login to access the full content or check if you have access via18.12.11.1.3 Method 3: By the Alkylation of Dithiocarbamates
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Gilchrist, T. L., Science of Synthesis, (2005) 18, 1044.
The S-alkylation of dithiocarbamate esters 138 is the method most widely used for the preparation of carbonimidodithioates. Dithiocarbamates are in turn made from amines and carbon disulfide under basic conditions, via the salts 137 or 140, so the method has several practical variations. These include “one-pot” procedures starting from compounds that incorporate the primary amino group, such as carboxamides, sulfonamides and cyanamides. The overall reaction sequence is outlined in Scheme 62.[67,203,224,267–273] Either symmetrically substituted diesters or unsymmetrically substituted diesters 139 can be prepared by an appropriate choice of conditions. Phenacyl chloride reacts with the salt 137 (R1 = NHTs; M = K) to give the 2-hydrazono-1,3-dithiolane 141 (yield 72%), which can be dehydrated to the dithiole 142 (Scheme 62); other α-halogenated ketones react similarly.[267]
Meeeee 88 Meeeeeeeee ee Meeeeeeeeeeeeeee[88,888,888,888,888–888]
| M8 | M8 | M8 | Meeeeeee Meeeeeee | Meeeeeee eee Meeeeeeeee | Meeee (%) ee 888 | Mee |
|---|---|---|---|---|---|---|
| Me | Me | Me | 888 | MeMM, MeM, ee | 88 | [888] |
| MM | Me | Me | 888 (M = M) | MeM, 8°M | 88 | [888] |
| MM | Me | Me | M8MMM | 8. MM8, MMM, 8°M; 8. Me8MM8 | 88 | [888] |
| MM | Me | 8-M8MM8M8MM8 | 888 (M = M) | 8. MeM, 8°M; 8. 8-M8MM8M8MM8Me | 88 | [888] |
| Me | Me | Me | MeMM8 | 8. MM8, MMM, 8°M; 8. MeM | 88 | [888] |
| 8-MeM8M8MM | Me | Me | 8-MeM8M8MMMM8 | 8. MeM, −88 ee 8°M; 8. MM8; 8. MeM | 88 | [888] |
| MM8Me | Me | Me | MeMM8MM8 | 8. MeMM, MM8, 8°M; 8. Me8MM8 | 88 | [888] |
| Me | MM8MM8Me | MM8MM8Me | MeMM8 | 8. MeMM, MM8, 8°M; 8. MeMM8MM8Me | 88 | [888] |
| MM8Me | Me | Me | 888 | MeMMM8M, ee | 88 | [88] |
| eeeeeeee-8-ee | Me | Me | eeeeeeee-8-eeeee | 8. MMM, MM8, ee; 8. MeM, 88°M | 88 | [888] |
Meeeeeeeeeee Meeeeeeee
Meeeeeee M-Meeeeeeeeeeeeeeeeeeeeeeee 888 eeee Meeeee M-Meeeeeeeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[888]
MMMMMMM: Meeeeeeeee, eeeeeeeee, ee eeeeeeeeee ee eeeeeeeeeee eeeeeee eee eeee eee ee eeeee.
88 M MeMM (8 eM, 8.88 eee) eee eeeee ee ee ee e eeeeeee eeee ee e eeeeee M-eeeeeeeeeeeeeeeeeee 888 (8.88 eee) ee MMM (88 eM). Meeee 8 e, MeM (8 e, 8.88 eee) eee eeeee eeeeeeee. Mee eeeeeee eee eeeeeee eee 8 e, eee eeee eeeeee eeee M8M (888 eM). Mee eeeeeee eee eeeeeeeee eeee eeeeee (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeee, eee eee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeee eee eeeee eeeeeeee.
Meeeeeee M-(8-Meeeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeee (888, M8 = 8-Meeeeeeeeeeeeee; M8 = M8 = Me) eeee Meeeeeeee-8-eeeeeeeeeee; Meeeeee Meeeeeeee:[888]
MMMMMMM: Meeeee eeeeeeeee ee eeeeeeeee eeeeeeeee, eee eeeee ee eeeeeeeeee, eeee eeeeeeeeee, eee eeeeeeeee.
MMMMMMM: Meeeeeee eeeeeee ee eeeeeeeee eee eeeeeeeeee ee eee eeee, eeee, eee eeeeeeeeeee eeeeee eee ee e eeeeeeee eeeee eeeeeeeeee.
Meeeeeeee-8-eeeeeeeeeee (8.8 e, 88 eeee) ee MMM (88 eM) eee eeeeeee eee eeeeee ee eee eeeee 88 M MeMM (8.8 eM, 88 eeee) eee eeeee, eeeeeeee ee MM8 (8.8 e, 8 eeee). Mee eeeeeee eeeeeeeee e eeeee eee eeeee. Meeee 88 eee, eeee 88 M MeMM (8.8 eM, 8 eeee) eee MM8 (8.88 e, 8.8 eeee) eeee eeeee eee, 88 eee eeeee, eeeeeee eeeeeeee ee 88 M MeMM (8.8 eM, 8 eeee) eee MM8 (8.88 e, 8.8 eeee) eeee eeeee. Mee eee eeee eee eeeeeee eee eee eeeeeee eee eeeeeee eee 8 e ee ee. Me eee eeeee eeeeee ee eee, eee Me8MM8 (8.88 e, 88 eeee) eee eeeee eeeeeeee. Meeee 88 eee, eee eeeeeeee eee eeeeeeee eee eee eeeee ee eee eeeeeee eeeeeee ee eeeeee. Mee eeeeeee eee eeeeeee ee ee eee 8 e, eee eeee ee eee eeeeee eeee M8M (88 eM). Mee eeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee M8M, eee eeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee (8.8 e) eee eeeeeeeeeeee (MeMM); eeeee: 8.88 e (88%); ee 888°M.
References
| [67] | Meeeeee, M.; Meeee, M., Meee. Mee., (8888) 888, 888. |
| [203] | Meeeeeeee, M.; Meeeeeee, M.; Meeeeee, M.; Meeeee, M., Meee. Mee., (8888) 88, 8888. |
| [215] | Meeeeee, M.; Mäeeee, M., Meee. Mee., (8888) 88, 8888. |
| [224] | Meeeeeee, M. M.; Meeešee, M.; Meeee, M.; Meeeeeeee, M. M., Meeeeee. Meeee. Meee. Meeeee., (8888) 88, 8888. |
| [267] | Meeeeee, M.; Meeeeeeee, M.; Meeee, M., Meeeeeeee, (8888), 888. |
| [268] | Meeee, M.; Meeeeeee, M.; Meeeeáe, M. M.; Meeee, M.; Meeeee, M., Meeeeeeee, (8888), 888. |
| [269] | Meeeee, M.; Meeeeee, M., M. Meeee. Meee. Meee., (8888) 888, 888. |
| [270] | Meeeeee, M.; Meeeeeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeee, M.; Meeeeeeeeee, M.; Meee, M.; Mee, M.; Meeeeeeee, M.; Meeeee, M., Meee. Meeee. Meee., (8888) 88, 8888. |
| [271] | Meee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeeeee, M., Meeeeeeee, (8888), 888. |
| [272] | Meeeeeee, M. M.; Meeeeeeeeee, M. M.; Meeeeee, M., Meeeeeeee, (8888), 888. |
| [273] | Meeee, M.; Meee, M., M. Meeeeeeeeee., M, (8888) 88, 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
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