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Synlett 2017; 28(19): 2675-2679
DOI: 10.1055/s-0036-1588533
DOI: 10.1055/s-0036-1588533
letter
Synthesis of Cyanamides from Cyanogen Bromide under Mild Conditions through N-Cyanation of Allylic Tertiary Amines
The authors are grateful to the National Natural Science Foundation of China (Grant NO.21576026) and the Joint Fund of the National Natural Science Foundation of China and the China Academy of Engineering Physics (Grant NO.11176004) for financial support.Weitere Informationen
Publikationsverlauf
Received: 05. Juni 2017
Accepted after revision: 09. Juli 2017
Publikationsdatum:
17. August 2017 (online)
Abstract
Cyanamides were selectively formed through a one-step nucleophilic substitution reaction of allylic tertiary amines with cyanogen bromide. Because of the mild reaction conditions and good yields of the reaction, as well as the commercial availability of the starting materials, this new method represents a valuable tool for the synthesis of cyanamides through an N-deallylation reaction and an N-cyanation reaction in one pot.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588533.
- Supporting Information
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References and Notes
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- 16 Piperidine-1-carbonitrile (1); Typical Procedure BrCN (4.4 mmol) was slowly added to a solution of N-allylpiperidine (4 mmol) in anhyd CHCl3 (5 mL) at r.t. under N2, and the mixture was then stirred for 24 h at r.t. until the reaction was complete (TLC). The mixture was then purified by column chromatography (silica gel, 10% EtOAc–PE) to give a colorless liquid; yield: 0.33 g (75%). IR (film): 2945, 2857, 2210 (C≡N), 1451 cm–1. 1H NMR (600 MHz, CDCl3): δ = 1.47 (m, 2 H), 1.53–1.54 (m, 4 H), 3.06–3.07 (m, 4 H). 13C NMR (150 MHz, CDCl3): δ = 118.6, 50.1, 24.5, 23.0. HRMS (ESI+): m/z [M + Na]+ calcd for C6H10N2Na: 133.073677; found: 133.073619.
- 17 4-Methylpiperazine-1-carbonitrile (10); Typical Procedure Prepared from 1-allyl-4-methylpiperazine (4 mmol) as for compound 1, and purified by column chromatography (silica gel, 2% MeOH–CH2Cl2) to give a colorless liquid; yield: 0.26 g (52%). IR (film): 2943, 2798, 2211 (C≡N), 1452, 1375, 1002, 787 cm–1. 1H NMR (600MHz, CDCl3): δ = 2.19 (s, 3 H), 2.36 (t, J = 5.4, 4.8 Hz, 4 H), 3.14 (t, J = 5.4 Hz, 4 H). 13C NMR (CDCl3, 150 MHz): δ = 117.6, 53.3, 48.9, 46.1. HRMS (ESI+): m/z [M + H]+ calcd for C6H12N3: 126.102620, found 126.102574.
- 18 Dimethylcyanamide (17) Prepared from N,N-dimethylprop-2-en-1-amine (4 mmol) as for compound 1, and purified by column chromatography (silica gel, 10% EtOAc–PE) to give a colorless liquid; yield: 0.20 g, (72%). IR (film): 2971, 2823, 2217 (C≡N), 1455, 1339, 1058, 762 cm–1. 1H NMR (600MHz, CDCl3): δ = 2.75 (s, 6 H). 13C NMR (150 MHz, CDCl3): δ = 119.3, 40.4. HRMS (ESI+): m/z [M + Na]+ calcd for C3H6N2Na: 93.042365; found: 93.042319.
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For reviews on cyanamides as building blocks in organic synthesis: see:
For reviews on the preparation of cyanamides from amines, see:
For reviews on the preparation of cyanamides from ketimines, see:
For reviews on transition-metal-catalyzed deprotection of allylic tertiary amines, see: