28073-03-2Relevant academic research and scientific papers
A newly developed synthesis of 1,3,5-trichlorobenzene (sym. TCB) from aniline
Mehilal,Salunke,Agrawal
, p. 604 - 607 (2007/10/03)
1,3,5-Trichlorobenzene (sym. TCB) has been synthesised by diazotisation of 2,4,6-trichloroaniline (sym. TCA) (by converting aniline into anilinium chloride followed by its chlorination) in the presence of H2SO4/NaNO2 and H3PO2. The reaction parameters for the synthesis of both sym, TCA as well as sym. TCB have also been established in order to get better purity and higher yields, sym. TCA and sym. TCB have been characterized by elemental analysis, Fourier Transform Infra Red (FTIR) and NMR spectroscopy. Further, different reaction parameters for the nitration of sym. TCB to get 1,3,5- trichloro-2,4,6-trinitrobenzene (TCTNB) and its amination to get pure 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) have also been established. A comparison of properties of TATB obtained from imported sym. TCB and from laboratory prepared sym. TCB validates the product.
Electrophilic Aromatic Substitution. Part 32. The Nitration of 1,3,5-Trichloro-2-nitrobenzene, 1,3,5-Trichloro-2,6-dinitrobenzene, and 1,2,3,5-Tetrachloro-4,6-dinitrobenzene in Sulphuric Acid and in Oleum
Moodie, Roy B.,Payne, Malcolm A.,Schofield, Kenneth
, p. 1457 - 1464 (2007/10/02)
The kinetics of nitration of 1,3,5-trichloro-2-nitrobenzene (TCNB) in sulphuric acid and in oleum at 25, 50, and 75 deg C, and of 1,3,5-trichloro-2,4-dinitrobenzene (TCDNB) in oleum at 150 deg C have been measured. 1,2,3,5-Tetrachloro-4,6-dinitrobenzene (TetCDNB) reacts with nitric acid in sulphuric acid and in oleum at 150 deg C; the rate profile for the reaction shows a nitration process to be occuring.From TCNB in sulphuric acid the yield of TCDNB was not quite quantitative and at 25 deg C in oleum a small amount of 1,2,3,5-tetrachloro-4-nitrobenzene was also formed.TCDNB gave a mixture of TCTNB (the major product) and TetCDNB in proportions which varied with acidity; lower acidities were more favourable to the formation of TetCDNB.The total amount of chlorine present in the TCDNB, TCTNB, and TetCDNB was equal to that present in the TCDNB at the start of the reaction.The nitration of TetCDNB in sulphuric acid at 150 deg C gave carbon dioxide and hydrogen chloride, and some sulphur dioxide and nitric oxide or nitrogen dioxide.In the nitration of TCDNB this compound produces the chlorinating agent and reacts with it to give TetCDNB.The chlorinating agent can chlorinate added 1,3-dinitrobenzene.The use of H(15)NO3 in the nitration TCDNB leads to (15)N-incorporation in it and in the TetCDNB produced.Separate nitration of TetCDNB causes only slight (15)N-incorporation into it.It is suggested that in addition to the main route of nitration leading to TCTNB, the nitration of TCDNB gives an ipso-Wheland intermediate by attack of nitronium ion at a nitrated position; this intermediate may either return to starting material or give a diene by nucleophilic capture.Decomposition of the diene gives hydrogen chloride or chloride anion which is oxidised by nitric acid to an electrophilic chlorinating agent.
Nitration of 1,3,5-Trichloro-2,4-dinitrobenzene: Nitro-denitration
Moodie, Roy B.,Payne, Malcolm A.,Schofield, Kenneth
, p. 233 - 234 (2007/10/02)
The title reaction effected in oleum at 150 deg C gives a quantitative yield based on chlorine of a mixture of 1,3,5-trichloro-2,4,6-trinitrobenzene and 1,2,3,5-tetrachloro-4,6-dinitrobenzene; the dependence of product ratios on acidity, effects of additives, and results of isotopic-labelling studies indicate that the latter product is formed via reversible ipso-attack of nitronium ion at a nitro substituted position followed by nucleophilic capture to give a diene which gives, possibly after oxydation, chlorine in an electrophilic form for reaction with starting material.
