PLANNED MAINTENANCE

There will be scheduled maintenance work beginning on Wednesday 26th February 2020 from 11:00 AM through to 12.00 PM (GMT).

During this time, you may not be able to log into ChemSpider Synthetic Pages. We apologise for any inconvenience this might cause and thank you for your patience.

Print version Print setup

Reduction of 2-methyl-6-nitro-1,3-benzothiazole to2-methyl-1,3-benzothiazol-6-amine; 2-methyl-1,3-benzothiazol-6-amine

SyntheticPage 916
Submitted Jan 10, 2020, published Jan 31, 2020
Robert Smith (rbsmith@uclan.ac.uk), Matthew C Jackson ()
A contribution from Smith Group


			Reaction Scheme: <IMG src="/images/empty.gif">Reduction of <SPAN id=csm1581940592372 title=2-methyl-6-nitro-1,3-benzothiazole class=csm-chemical-name>2-methyl-6-nitro-1,3-benzothiazole</SPAN> to<SPAN id=csm1581940601536 title=2-methyl-1,3-benzothiazol-6-amine class=csm-chemical-name>2-methyl-1,3-benzothiazol-6-amine</SPAN><IMG src="/images/empty.gif">

Chemicals Used

2-Methyl-6-nitrobenzothiazole (See page 915)

Tin (II) Chloride (Sigma Aldrich)

Hydrochloric Acid (Fisher Scientific)

Procedure

To a 250 mL wide necked conical flask was added 2-methyl-6-nitrobenzothiazole (5.24 g, 27 mmol), and hydrochloric acid (6M, 150 mL). The solution was stirred until all the solid had dissolved, then tin (II) chloride dihydrate (33.3 g, 148 mmol) was added slowly with constant stirring, producing a white precipitate. Upon total addition of the tin (II) chloride dihydrate, the reaction was continued to stir at 100°C for 3 hours*. After this time the mixture was allowed to cool and then the pH was adjusted to pH=8** via the slow addition of sodium hydroxide pellets. The solid precipitate produced on neutralisation, was isolated by vacuum filtration and washed with ethyl acetate (300 mL), the mixture was extracted with ethyl acetate (800 mL) and the combined organic phases were dried with sodium sulphate, filtered and evaporated to dryness to afford 2-methyl-1,3-benzothiazol-6-amine (2.78 g, 63%) as a rose white solid.

Author's Comments

*A conical flat bottomed flask fitted with a reflux condenser.  The temperature what controlled using the sensor on the hot plate.  Stirring was accomplished using a stirring bar, which was controlled from the hot plate.  The whole reaction was accomplished in the open air without the need of dry/inert conditions.

** Universal indicator paper was used to monitor the change in pH to pH=8.

Data

1H NMR (300 MHz, DMSO-d6) δ 7.56 (d, J = 8.6 Hz, 1H), 7.03 (d, J = 1.8 Hz, 1H), 6.74 (dd, J = 8.6, 1.8 Hz, 1H), 5.32 (s, 2H), 2.66 (s, 3H). 13C NMR (75 MHz, DMSO) δ 175.09, 157.25, 144.54, 136.40, 122.77, 121.86, 119.60, 20.72. GC-MS (EI) m/z: 164.01.


Lead Reference

Demeter, O., Kormos, A., Koehler, C., Mezö, G., Németh, K., Kozma, E., Takács, L.B., Lemke, E.A., Kele, P. Bisazide Cyanine Dyes as Fluorogenic Probes for Bis-Cyclooctynylated Peptide Tags and as Fluorogenic Cross-Linkers of Cyclooctynylated Proteins (2017) Bioconjugate Chemistry, 28 (5), pp. 1552-1559.

Supplementary Information

1H NMR: 2941-62-0 (Proton NMR.pdf)
13C NMR: 2941-62-0 (Carbon NMR.pdf)
GCMS: 2941-62-0 (GC-MS.pdf)
IR: 2941-62-0 (IR.pdf)

This page has been viewed approximately 107 times since records began.

Get structure file (.cdx, .sk2, .mol)

Keywords: amines, aromatics/arenes, heterocyclic compounds, reduction

Post new comment
Loading ...