Properties and Synthetic Utility of N-Substituted Benzotriazoles.

Synthesis and properties of new substituted 1,2,4-triazoles: potential antitumor agents

5.3. Aromatic Ring Formation 1576 5.3.1. One Substituent at C-2 1576 5.3.2. Two Substituents at C-2 and C-3 1577 5.3.3. Two Substituents at C-2 and C-5 1577 5.3.4. Two Substituents at C-3 and C-4 1577 5.3.5. Three Substituents at C-2, C-3, and C-4 1578 5.3.6. Four Substituents at Carbon Atoms 1579 5.3.7. Benzotriazolyl Substituent at the Ring 1579 6. Furan 1580 6.1. Nonaromatic Rings 1580 6.1.1. Tetrahydrofurans 1580 6.1.2. 2,5-Dihydrofurans 1580 6.2. Electrophilic Substitution of the Aromatic Ring 1581 6.3. Aromatic Ring Formation 1582 7. Thiophene 1583 7.1. Nonaromatic Rings 1583 7.2. Electrophilic Substitution of the Aromatic Ring 1583 7.3. Aromatic Ring Formation 1583 8. Five-Membered Rings with Two Heteroatoms 1584 8.1. Pyrazole 1584 8.2. Imidazole 1586 8.3. Isoxazole 1589 8.4. Oxazole 1590 8.5. Thiazole 1592 9. Five-Membered Rings with Three or Four Heteroatoms 1594

Synthesis of Heterocycles Mediated by Benzotriazole. 1. Monocyclic Systems

An efficient and straightforward copper-catalyzed method allowing vinylation of N- or O-nucleophiles with di- or trisubstituted vinyl bromides is reported. The procedure is applicable to a broad range of substrates since N-vinylation of mono-, di-, and triazoles as well as O-vinylation of phenol derivatives can be performed with catalytic amounts of copper iodide and inexpensive nitrogen ligands 3 or 8. In the case of more hindered vinyl bromides, the use of the original bidentate chelator 8 was shown to be more efficient to promote the coupling reactions than our key tetradentate ligand 3. The corresponding N-(1-alkenyl)azoles and alkenyl aryl ethers are obtained in high yields and selectivities under very mild temperature conditions (35-110 degrees C for N-vinylation reactions and 50-80 degrees C for O-vinylation reactions). Moreover, to our knowledge, this method is the first example of a copper-catalyzed vinylation of various azoles. Finally, this protocol, practical on a laboratory scale and easily adaptable to an industrial scale, is very competitive compared to the existing methods that allow the synthesis of such compounds.

Mild Copper‐Catalyzed Vinylation Reactions of Azoles and Phenols with Vinyl Bromides

4.01 – 1,2,3-Triazoles

The N-chloromethyl group of 1-(chloromethyl)benzotriazole undergoes nucleophilic substitution by carbon, nitrogen, phosphorus, oxygen, and sulphur nucleophiles. α-Lithiation was achieved in high yield in 1-phenylthiomethyl-, 1-phenylsulphinylmethyl-, and 1-(phenylstilphonylmethyl)benzotriazoles and the lithio derivatives reacted with a variety of electrophiles. New benzotriazolium salts were prepared by quaternization of the N-3 nitrogen with methyl iodide.

The chemistry of N-substituted benzotriazoles. Part 1.1-(Chloromethyl)benzotriazole

Substitutions nucleophiles du chloromethyl-1 benzotriazole avec des nucleophiles de C, N, P, O et S; α-lithiation et reactions electrophiles du phenylthiomethyl-1 benzotriazole et des sulfoxyde et sulfone correspondants; quaternarisation du N-3 de benzotriazoles

Fatma Mahni

Papers

The chemistry of N-substituted benzotriazoles. Part 1.1-(Chloromethyl)benzotriazole

The chemistry of N-substituted benzotriazoles. I: 1-(Chloromethyl)benzotriazole

The Chemistry of N-Substituted Benzotriazoles. Part 1. 1-(Chloromethyl)benzotriazole.