Sulfurated sodium borohydride reacts with benzylic halides to give high yields of α-toluenethiol or benzylic polysulfldes depending upon the experimental conditions and the mode of hydrolysis.Aliphatic halides and dibenzylic halides react in the same manner as benzylic halides for a given experimental condition whereas benzylic halides substituted with other groups can be totally or partially reduced depending on the stability of the substituent towards NaBH2S3.Halogens directly attached on the aromatic ring do not react with NaBH2S3.

The following substrates react with sulfurated sodium borohydride, NaBH2S3, to give the corresponding products as shown by the formulas in parentheses: azobenzene [Formula: see text], azoxybenzene [Formula: see text], phenyl isocyanate (C6H5NH2, C6H5NHCH3), N-nitrosodiphenylamine ((C6H5)2NH, (C6H5)2NNH2), diphenylcarbamyl chloride ((C6H5)2NH), phenyl isothiocyanate (C6H5NH2), benzyl carbamate (C6H5CH2OH), benzyl N-phenylcarbamate (C6H5CH2OH, C6H5NH2, C6H5CH2SH), benzyl nitrite (C6H5CH2OH), benzyl nitrate (C6H5CH2OH), benzyl thiocyanate (C6H5CH2S2CH2C6H5), and pyridine-1-oxide (C5H5N). Benzotriazole, pyridine, phthalimide, and N,N′-diphenylurea were found to be stable towards NaBH2S3.The advantage of sulfurated sodium borohydride, NaBH2S3, over sodium borohydride, NaBH4, as a reducing agent was also proven when it was found that most of the above substrates were inert toward NaBH4 except for the following organic nitrogen compounds which reacted with NaBH4 to give the products indicated in parentheses: N-nitrosodiphenylamine ((C6H5)2NH), diphenylcarbamyl chloride ((C6H5)2NCH3), phenyl isothiocyanate (C6H5NHCH3), benzyl N-phenylcarbamate (C6H5CH2OH, C6H5NHCH3), and benzyl thiocyanate (C6H5CH2-S2CH2C6H5).

Untersuchungen zeigen, daß das sulfurierte Na‐borhydrid gegenüber organischen N‐ Verbindungen ein ausgezeichnetes Reduktionsmittel ist.

Die Reaktion von Benzylfluorid, ‐chlorid, ‐bromid bzw. ‐jodid mit NaBH2S3 (NBHS) und anschließende Hydrolyse mit 10%iger HCl oder NaOH liefern Benzylmercaptan, Mono‐, Di‐ und Polysulfide, wobei die Produktverteilung von dem Molverhältnis der Reaktanten, von der Temperatur und Art der Hydrolyse bestimmt wird.

p‐Tolüolsulfonsäure im Bombenrohr ergxbt neben den Fumarsäureestern (II) auch die umgelagerten Ester (III).