(Hive Addict)
06-22-04 00:21
No 514671
(Rated as: good read)
Patent US3686300
Example 1
Into a 1l content, 4-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a gas-delivery tube, a heating and a cooling bath, 176g (1.5 mols) of chlorosulfonic acid were admitted to which 24g (0.45 mol) of ammonium chloride were portionwise added. In doing so, hydrogen chloride escaped and the solution warmed to about 50°C. Thereupon, at 80°C, 92,1g (1 mol) of toluene were dropwise added within 2 - 3h. Subsequently, the batch was cooled to about 35°C and 176g (1.5 mols) of chlorosulfonic acid were introduced within 5 - 10 min. The whole was stirred at the said temperature for 1h and the reaction mixture poured onto iced water. To determine the yield, the p-toluene-sulfochloride formed was taken up in methylene chloride, was washed, dried and distilled in vacuo. Besides 2g of residue from distillation 161g of p-toluenesulfochloride were obtained (84-85%) having a solidification point of 62°C. The portion of para compound was thus amounted to 90%, the theoretical yield in para-compound to 77%.
Example 2
Into the reaction vessel 199g (1.7 mols) of chlorosulfonic acid were admitted and 27g (0.5 mol) of ammonium chloride added thereto with stirring. Thereupon, at 80-85°C 92.1g of toluene were dropwise added and, subsequently thereto, at 35°C, 152g (1.3mols) of chlorosulfonic acid were allowed to run into the mixture. Work-up was effected as in Example 1. It yielded 152g (80%) of p-toluenesulfochloride whose solidification point was 62.5°C. The portion of para compound amounted to 90-92%, the theoretical yield thereof to 72-74%.
The following table lists further examples wherein 1 mol of toluene was reacted with 3 mols of chlorosulfonic acid and in which 1.5 mol always of chlorosulfonic acid was used.
| mols | salt | temp °C | yield | mp °C | % p-TsCl |
| 0.25 | Na2SO4 | 65 | 78.3 | 61 | 88 |
| 0.2 | Na2SO4 | 75 | 70.4 | 62.5 | 90-92 |
| 0.45 | NaCl | 70 | 80 | 60 | 86 |
| 0.2 | K2SO4 | 70 | 83.5 | 61 | 88 |
| 0.2 | K2SO4 | 80 | 77 | 62 | 89-91 |
| 0.4 | KCl | 70 | 83 | 61 | 88 |
| 0.4 | Na2SO4 | 80 | 83 | 61.5 | 88-89 |
| 0.4 | KCl | 90 | 78.5 | 62 | 89-91 |
| 0.2 | (NH4)2SO4 | 70 | 81.7 | 61 | 88 |
| 0.14 | Na2SO4 | 75 | 80 | 62 | 89-91 |
J.Amer.Chem.Soc., 115,8.1993;3049
4-toluenesulfonylchloride
To 1ml (15mmol) of chlorosulfonic acid in a 25mL 3-neck round-bottom flask fitted with a reflux condenser, syringe adapter and stopper was added 0.8g (15mmol) of ammonium chloride. The mixture was heated to 80°C and 1mL (8.6 mmol) of toluene added over 0.5h. The reaction was then cooled to 35°C and another 1mL of chlorosulfonic acid was added; the reaction mixture was stirred for an additional half hour. The mixture was poured onto 30mL of ice and extracted with 3 x 10mL of DCM. The organic layer was washed with 10% NaHCO3 and water and then dried over MgSO4 and filtered. The solvent was removed by rotary evaporation, yielding white crystals (54%). The isolated material contained 92% of the para isomer and 8% of the ortho form.
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(Hive Addict)
06-22-04 20:25
No 514803
Patent DE385049
Example 2
70 parts finely ground NaCl are introduced to 300 parts 60% oleum. Then, whith cooling and under good stirring, 92 parts toluene are added. The whole is stirred for some hours and poured on ice, whereupon the mixture of isomeric tosylchlorides (140 parts) precipitates and is worked up as usual.
Would anyone object, that for alkylation purposes o-/p-TsOAlk are equally usable ?
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(Hive Addict)
06-22-04 20:46
No 514806
Patent DE98030
100kg toluene are slowly introduced to 400kg of chlorosulfonic acid, cooled to 0°C, with constant stirring, care being taken that the temperature doesn't exceed 5°C. After the toluene addition is complete, the mixture is stirred for 12h at 0-5°C. The mixture is then poured on ice, the toluenesulfochlorides form their own layer and are separated by decantation. After the TsCl-layer has been cooled to -20°C for 12h the p-TsCl crystallized and is removed from the o-TsCl by suctin filtration. Yield: 100%, ortho:para=60%:40%.
--psyloxy--
(Hive Addict)
06-22-04 21:03
No 514809
Bull.Soc.Chim.Fr., 39,4.1926;316Je ne parelé pas francaise ... but: Ph-SO3Na + HSO3Cl __> Ph-SO2Cl in 65% - TsOH __> TsCl, same procedure, same yield.
J.Gen.Chem.USSR, 52,2.1982;341-343non too informative article, but yields are given when only 1.2 equiv. of HSO3Cl are used. Actual procedure is in a russian ref.
Chem.Ber., 12.1879;1849-1850An old German article, only 50% yield. Rests here so nobody thinks there's better methods out there then presented in the patents above.
Just in case you didn't notice: Post 514474 (psyloxy: "chlorosulphonic acid", Chemistry Discourse)
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