该类反应属于典型的亲核取代反应，按照反应历程分两种类型：单分子的亲核取代 反应(SN1) 和双分子的亲核取代反应(SN2)。  

       单分子的亲核取代反应(SN1)历程中反应速度只与反应底物卤代物的浓度有关，与碱 的浓度无关。因此，从动力学上讲它是一个一级反应。例如溴代叔丁烷的水解： 

       此反应是分两步进行,第一步是反应物在溶剂中首先离解成叔丁基正离子和溴负离:

第二步则是生成的叔丁基碳正离子再与 HO-作用,生成叔丁醇: 

       另一类为双分子的亲核取代反应(SN2)，它的水解速度与卤代烃的浓度和碱的浓度成 正比，因此该类反应是一个二级反应。例如溴甲烷的水解：

       反应过程中 C-Br 键的断裂与 C-O 键的形成是同时进行的。当进攻试剂 HO- 从离去基团 Br 的背后进攻中心碳原子时(这是比较有利的进攻方式)。此时，HO- 、Br 和中心碳原子 几乎处于同一直线上，形成一个“过渡态”。而中间碳上的三个 H 原子则处于垂直于这 个直线的平面上，当 HO-与中心碳原子进一步接近，终形成一个稳定的 C-O 键时， C-Br 也彻底断裂，生成 Br-离子，同时中心碳上的三个 H 原子也向后翻转，使碳原子恢 复成原来的 sp3 杂化状态。从立体化学上来看，在反应过程中发生了构型的转化，使得产物与原来的反应物构型正好相反，这也正是在 1893 年发现的瓦尔登(Walden)转化。另 外许多反应，卤代物直接水解并不是太好，因此一般先用 AcO－取代，而后再水解得到 相应的醇。  

卤代烃的水解反应制备醇示例 

    Combined the material with 75% DMF, 1.2 equiv of NaOH were stirred for 30 min at room temperature. And recrystallized from MeOH to give the colourless needles (95% yield)。

卤代烃的水解反应制备醇示例 

    Water (100mL) and CaCO3 (18g, 180mmol) were added into a solution of 10.5g (35mmol) of 1-bromo-2-(bromomethyl)naphthalene in 100mL of p-dioxane ,and the mixture was refluxed for 10hrs. The solution was cooled and the dioxane removed under reduced pressure. Methylene chloride (200mL) was added followed by treatment with dilute HCl until all solid had dissolved .The organic phase was separated, washed with NaHCO3 solution, dried over MgSO4, and filtered. Removal of the solvent left a white solid, which was recrystallized from hexane to give 7.9g of (1-bromonaphthalen-2-yl)methanol (95% yield)

卤代烃的 AcO－取代示例

     A 150 g portion of the thus obtained 1-chloro-(E,Z)-7,9-dodecadiene was admixed with 150 g of anhydrous potassium ace-tate and 100 g of acetic acid and the mixture was heated at 160 .deg.C for 6 hours under agitation in an atmosphere of nitrogen to convert the chloride into acetate.. After completion of the reaction, the reaction mixture was poured into a large volume of water and the organic phase taken by phase separation was distilled under reduced pressure to give 80 g of 7,9-dodecadienyl acetate of which the purity of the E,Z-isomer was at least 75percent. 

 酯水解得到相应的醇示例 

    2N sodium hydroxide (40 ml) was added to a solution of 5-(2-acetoxyethyl)-2-methyl-4-phenyloxazole (16.6 g) in methanol (40 ml) and the mixture was stirred for 30 minutes, diluted with water and extracted with ethyl acetate..The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was then distilled off and the residue wwas purified by silica gel chromatography (silica gel: 190 g, eluent: isopropyl ether) to give an oil of 5-(2-hydroxyethyl)-2-methyl-4-phenyloxazole, yield 11.7 g (84.8percent).NMR (CDCl3) : 　 2.40 (3H, s), 3.07 (2H, t), 3.20 (1H, broad), 3.97 (2H, broad), 7.23-7.80 (5H, m).