A kind of 3-substituted dibenzothiophene and its synthetic method
A dibenzothiophene and synthesis method technology, applied in the direction of organic chemistry, etc., can solve the problems of unsuitable process for mass production operation, inability to obtain high-purity final products, a large amount of waste acid and waste water, etc., and achieve simplified post-treatment methods, Low pollution and low equipment requirements
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[0037] The invention discloses a method for synthesizing 3-substituted dibenzothiophene, comprising the following steps:
[0038] Step 1: take o-iodoanisole and 4-substituted phenylboronic acid as starting materials, carry out a coupling reaction to obtain intermediate a, and the molar ratio of the o-iodoanisole and 4-substituted phenylboronic acid is 1:1 ~1.4;
[0039] Step 2: The intermediate a, p-toluenesulfonic acid and hydrogen peroxide are oxidized to obtain the intermediate b, and the molar ratio of the intermediate a, p-toluenesulfonic acid and hydrogen peroxide is 1:0.5:1~1.2;
[0040] Step 3: Ring-closing reaction of intermediate b and Eaton reagent to obtain 3-substituted dibenzothiophene, the molar ratio of intermediate b to Eaton reagent is 1:1~1.5; The structural formula is , where R is Br, F, Cl, CF 3 , OH, benzene or NO 2 .
[0041]The Eaton reagent is a 7.7 wt% solution of phosphorus pentoxide in methanesulfonic acid, which can replace polyphosphoric aci...
Embodiment 1
[0053]
[0054] Among them, it is o-iodoanisole and phenylboronic acid.
[0055] Step 1: under nitrogen protection, add o-iodoanisole sulfide (2.50kg, 10mol), phenylboronic acid (1.46kg, 12mol), toluene 10L, ethanol 5L, water 5L, potassium carbonate (2.76kg, 20mol) to the reaction flask. ), added, stirred, heated to 60~70°C, rapidly added tetrakis(triphenylphosphine)palladium (115g, 0.1mol), continued to heat up to 75~80°C and refluxed for 10h, the reaction was completed, cooled, and toluene was used. The reaction system was extracted, the organic phase was washed with water, the organic phase was dried, filtered to remove the desiccant, the organic phase was concentrated, the concentrate was recrystallized with methanol to HPLC>98.5%, and dried to obtain intermediate a-1 with a yield of 90.2%.
[0056] Step 2: Add the intermediate a-1 (1.80kg, 9mol) and p-toluenesulfonic acid (0.856g, 4.5mol) prepared in the previous step into the reaction flask, add 7.2L of dichloroethane...
Embodiment 2
[0060]
[0061] in, is o-iodoanisole, For p-bromophenylboronic acid.
[0062] Step 1: under nitrogen protection, add o-iodoanisole (2.5kg, 10mol), p-bromophenylboronic acid (1.46kg, 12mol), toluene 10L, ethanol 5L, water 5L, potassium carbonate (2.76kg) to the reaction flask. , 20mol), after adding, stirring, heating to 60~70°C, rapidly adding tetrakis(triphenylphosphine)palladium (115g, 1mol), continuing to heat up to 75~80°C for refluxing reaction for 10h, the reaction was completed, cooling, using The reaction system was extracted with toluene, the organic phase was washed with water, the organic phase was dried, filtered to remove the desiccant, the organic phase was concentrated, the concentrate was recrystallized with methanol to HPLC> 97.8%, and dried to obtain intermediate a-2 with a yield of 65.5%.
[0063] Step 2: Add the intermediate a-2 (1.30kg, 6mol) and p-toluenesulfonic acid (0.570kg, 3mol) prepared in the previous step into the reaction flask, add 5.4L o...
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