Hydrogen Peroxide → Sodium selenide

The approach used for the synthesis of ethylhexyl 4,6-dibromoselenolo[3,4-b]thiophene carboxylate monomer 7 is based on a modified reported procedure (Scheme 1). Sodium selenide was prepared by slow addition of sodium borohydride to a mixture of selenium powder in a basic aqueous solution. The resulted colorless aqueous Na2Se solution was added dropwise into an ethanolic solution of 2,3-bischloromethyl-5-carbomethoxyselenophene 1 over 30 minutes to produce the dimer of 2 in 73% yield as the only product. The structure was verified by 1H NMR and mass spectrum showed the exact molecular ion at 592 and the base peak at 296. The formation of 3 was not observed since the Na2Se solution was added at a faster rate typical to these types of cyclizations. Following the reported procedure would lead to the formation of 2 as a major product (˜70%) and 3 as a minor product (˜10%). Since compound 3 is the key starting material, the need to improve its yield is required. Thus, several different experimental conditions were used including the use of NaHSe or Na2Se in polar solvents (ethanol, water and THF), changing the mode of addition and the temperature at which reagents were added, the result is the formation of 2 as the sole product or as a major product and 3 as the minor one. It has been reported that the benzene analogue of dimer 2 can be converted into the corresponding dihydrobenzoselenophene thermally or photochemically in quantitative yields. This may be formed by favorable intramolecular cyclization of a biradical intermediate into two of the five-membered ring. Accordingly, flash pyrolysis of dimer 2 under reduced pressure was converted to dihydroselenoselenophene 3 in good yields (56%). The overall yield of the first two steps is 41% which is about four times the previously reported approach (10-12%). All spectroscopic data were in accordance with those for methyl 4,6-dihydroseleno[3,4-b]selenophene-2-carboxylate (3) reported. Aromatization of 3 by oxidation using H2O2 to give the N-selenoxide which upon careful treatment with cold acetic anhydride gave the corresponding methyl selenolo[3,4-b]thiophene carboxylate 4. Addition of acetic anhydride without cooling would lead to decomposition of some of the starting material due to instant spontaneous exothermic reaction that takes place. Bromination using NBS gave the methyl 4,6-dibromoselenolo[3,4-b]thiophene carboxylate 5 which upon hydrolysis under basic conditions yielded 4,6-dibromoselenolo[3,4-b]thiophene carboxylic acid 6. To enhance the solubility of the polymer, carboxylic acid 6 was esterified by the branched 2-ethyl-1-hexanol using DCC and DMAP to give the corresponding ethylhexyl 4,6-dibromoselenolo[3,4-b]thiophene carboxylate 7 monomer in high yield (88%).

1. customto produce the dimer of 2 in 73% yield as the only product
2. additionwas added at a faster rate typical to these types of cyclizations
3. customyield
4. additionthe mode of addition
5. additionthe temperature at which reagents were added
6. customThis may be formed by favorable intramolecular cyclization of a biradical intermediate into two of the five-membered ring
7. customin good yields (56%)

ORD record

ord-de3ec9617d494c2e9094100d88a8d18a

Source dataset

uspto-grants-2015_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09153785B2