通过金属试剂与二氧化硫/NCS或氯化亚砜或氯化砜反应，也是常有的制备芳香磺酰氯的重要方法。

从操作过程上讲，该法可分为两类：

方法一：芳基卤化物经丁基锂处理，得到相应的芳基金属化合物，然后通入二氧化硫，再用NCS或氯化亚砜氯代，可以制备相应的磺酰氯。此方法自从发现以来应用广泛。除丁基锂外，其他金属试剂如Grignard 试剂，铜试剂等，也可用于制备芳基金属化合物[1, 2-6]。

方法二：使用芳基理化物直接和氯磺酰氯反应制备相应的磺酰氯。这种方法操作方便，收率中等[6]。

实例一：

To a solution of 1-bromo-4-methoxybenzene (64.2 g, 0.247 mol) in dry THF (300 mL) was added  n-BuLi (138 mL, 0.346 mol) at -70 oC under N2 atmosphere.  The mixture was stirred at -70 oC for 30 min, which was added to a solution of SO2 (644 g,6.92 moL) in dry THF (1000 mL) at -70 oC through a cannula. The mixture was stirred at room temperature overnight. The mixture was concentrated under reduced pressure. The residue was triturated with EtOAc (300mL) and filtered to give the crude lithium arylsulfinate.

To a solution of lithium arylsulfinate (44 g, 0.247 mol) in dry CH2Cl2(600 mL) was added SO2Cl2 (66 g, 0.5 mol) dropwise at 0 oC. The mixture was stirred at room temperature overnight.  Then the mixture was concentrated under reduced pressure and the residue was triturated with dry THF (3 L x 4) and filtered, the filtration was concentrated under reduced pressure, the residue was recrystallized from n-hextane to give a colorless crystal (48.1 g, 95%). (Tatsuo, H. Synthesis 1986, 10, 852.)

实例二：

To a solution of 2, 6–diphenyliodobenzene (1.42 g, 4 mmol) in Et2O was added dropwise BuLi (2.56 mL, 1.56 Min hexane, 4 mmol) at 0 oC. The mixture turned yellow and a white solid precipitated. After the mixture was stirred for 8 h at room temperature, the freshly distilled sulfurylchloride (0.643 mL, 8 mmol) was added slowly at -78 oC. The mixture was stirred overnight at room temperature, cooled to 0 oC, poured onto 1 M HCl, and extracted with Et2O. The organic layer was washed with water and brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was recrystallized from CHCl3–hexane to give the corresponding arene sulfonyl chloride (0.91 g，yield：70%).（Kosugi, Y et al. Tetrahedron 2007, 63, 6191.）

【参考文献】

[1] Tatsuo, H. Synthesis1986, 10, 852.

[2] Gilbrrt,E.E. Synthesis 1981，60，124.

[3] Quast, H et al. Synthesis1974, 489.

[4] Cahiez, G.. J. Organomet.Chem. 1976, 121, 123.

[5] Pinnick, H. J.Org. Chem. 1979, 44, 160.

[6] Gyula, L. Eur.J. Org.Chem. 2004, 4130.