Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 5876-51-7, name is 5-Iodobenzo[d][1,3]dioxole, This compound has unique chemical properties. The synthetic route is as follows., Quality Control of 5-Iodobenzo[d][1,3]dioxole
[00216] This example demonstrates that palladium catalysts can be activated by treatment with a base prior to their use in promoting the reaction of an organic halide with a dialkoxyborane. In particular, the catalytic activity of PdCl2(dppf).CH2Cl2 can be increased significantly, especially the initial activity, by treatment, in the reaction solvent, with triethylamine prior to the addition of the pinacolborane and substrate. Besides the rate enhancement observed in the formation of the required product boronic acid ester (e.g. pinacol ester of 3,4-methylenedioxyphenylboronic acid) there is a further advantage in the prior activation of the catalyst in that the amount of bi-product formed in the reaction (viz. 1,3-benzodioxole through dehalogenation of the substrate and the pinacol ester of phenylboronic acid in which the phenyl groups are from the catalyst ligand) is significantly reduced. Formation of 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole [00217] [C00024] [00218] To 24.6 mg PdCl2(dppf).CH2Cl2 in a reaction tube under nitrogen was added 4 ml dioxane and 0.42 ml (3 mmol) triethylamine. The mixture was heated at 80 C. for ca 17 h. The red-orange suspension of PdCl2(dppf).CH2Cl2 dissolved to give a dark red-brown solution. To this solution, at room temperature, was added 0.23 ml (1.5 mmol) pinacolborane and 253 mg (1.02 mmol) 1-iodo-3,4-methylenedioxybenzene. The reaction solution was warmed to 80 C. with stirring for 1 h in an oil bath. The solution remained a dark red-brown in colour. An aliquot (ca. 0.25 ml) of the reaction solution was removed, extracted into ethyl acetate and washed several times with water and brine solution and analysed by gc (fid detector, SGE HT5 capillary column). Apart from a small amount of 1,3-benzodioxole (5% of uncorrected gc peak area) and pinacol ester of phenylboronic acid (3%), the only other product peak in the gc (area of 92%, uncorrected) was that due to the desired arylboronic acid pinacol ester. There was no evidence of biaryl formation. The rate of reaction of 1-iodo-3,4-methylenedioxybenzene with pinacolborane at 80 C. with activated catalyst is indicated also in Table 17.1. Table 17.2 shows that side product formation can be reduced still further by carrying out the reaction at 30 C. [TABLE-US-00002] TABLE 17.1 Rate of product formation on reaction* of 1-iodo-3,4-methylenedioxybenzene with pinacolborane at 80 C. in which the catalyst, PdCl2(dppf).CH2Cl2, was activated, prior to employment in the reaction, with triethylamine. The concentrations are expressed in area % (uncorrected for response factors) determined by gc analysis of aliquots of the reaction solution taken at selected reaction times. Reaction Time (mins) [C00025] [C00026] [C00027] [C00028] 6 4.4 0.74 54 40 10 4.4 1.0 40 55 15 5.2 2.1 26 66 20 5.9 2.9 16.3 75 25 5.7 2.9 9.2 82 30 6.0 3.2 3.6 87 35 5.9 3.4 1.2 89 40 5.7 3.4 0.7 90 50 5.6 3.4 0 91 180 5.7 3.5 0 91 *Used 25.5 mg of PdCl2(dppf).CH2Cl2. 4 ml dioxane, 0.43 ml (3.0 mmol) triethylamine and warmed to 80 C. for 16 h. Then added 0.23 ml (1.5 mmol) pinacolborane and 247 mg (1.0 mmol) 1-iodo-3,4-methylenedioxybenzene at room temp. before warming the reaction to 80 C. The reaction was quenched at the selected reaction time by addition of the aliquot of reaction solution to a water/ethyl acetate mixture. [TABLE-US-00003] TABLE 17.2 Rate of product formation on reaction* of 1-iodo-3,4-methylenedioxybenzene with pinacolborane at 30 C. in which the catalyst, PdCl2(dppf).CH2Cl2, was activated, prior to employment in the reaction, with triethylamine. The concentrations are expressed in area % (uncorrected for response factors) determined by gc analysis of aliquots of the reaction solution taken at selected reaction times Reaction Time (h) [C00029] [C00030] [C00031] [C00032] 1 1.6 0 94 4.8 2 1.7 0 89 9.7 3 2 0 84 13.8 4 2 0 81 17 7 2.3 0 71 26 28 4 0.6 27 68 71.5 4.2 1.9 0 94 *Used 25 mg of PdCl2(dppf).CH2Cl2, 4 ml dioxane, 0.43 ml (3.0 mmol) triethylamine and warmed to 80 C. for 16 h. Then added 0.23 ml (1.5 mmol) pinacolborane and 262 mg (1.05 mmol) 1-iodo-3,4-methylenedioxybenzene at room temp. before warming the reaction to 80 C. The reaction was quenched at the selected reaction time by addition of the aliquot of reaction solution to a water/ethyl acetate mixture. [00219] When the catalyst PdCl2(dppf).CH2Cl2 is treated with the amine together with the borane ester prior to use in the reaction, the initial reaction rate is enhanced, indicating that some catalyst has been activated. The overall reaction, however, is slower than that when the catalyst receives no pretreatment. Catalyst presumably unactivated by the pretreatment with triethylamine and pinacolborane appears to be more resistant to activation during the progress of the boronation reaction. This can be seen by comparison of Tables 17.3 and 17.4. In Table 17.3, the catalyst was not activated prior to use and the reaction rate over the first 1 to 2 hours is slow. In T…
According to the analysis of related databases, 5876-51-7, the application of this compound in the production field has become more and more popular.
Reference:
Patent; Commonwealth Scientific and Industrial Research Organisation; US6680401; (2004); B1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com