Process for producing an aminopropyne or enaminone

Patent metadata

Field	Value
Publication number	US-9193668-B2
Application number	US-201214131083-A
Country	US
Kind code	B2
Filing date	Jul 6, 2012
Priority date	Jul 6, 2011
Publication date	Nov 24, 2015
Grant date	Nov 24, 2015

Abstract

There is provided a process for producing an aminopropyne or an enaminone comprising the step of reacting a metal acetylide, an amine and a carbonyl-containing compound in the presence of a transition metal catalyst. There is also provided a process for producing an aminopropyne comprising the step of reacting a metal acetylide, an amine and a halide-containing compound in the presence of a transition metal catalyst at a reaction temperature of 50° C. to 150° C. There are also provided processes to further synthesize the aminopropyne produced to obtain a butyneamine, another aminopropyne or a triazol.

First claim

The invention claimed is:

1. A process for producing an aminopropyne comprising the step of reacting a metal acetylide, a primary or secondary amine and a ketone or an aldehyde in the presence of a transition metal catalyst;
wherein:
the metal acetylide is selected from the group consisting of calcium carbide (CaC 2 ), lithium acetylide (Li 2 C 2 ) and lanthanium acetylide (LaC 2 ); and
the transition metal of said transition metal catalyst is selected from the group consisting of copper, silver and gold; wherein when the transition metal is copper the transition metal catalyst is selected from the group consisting of copper chloride, copper bromide, copper iodide, copper fluoride, copper acetate and copper acetylacetonate.

2. The process as claimed in claim 1 , wherein said aminopropyne has a terminal alkyne group.

3. The process as claimed in claim 1 , wherein the aldehyde has the structure R 1 CHO, where R 1 is selected from aryl or C 1-5 -alkyl, said aryl being optionally substituted by at least one of halide, nitrile, C 1-5 -alkyl, C 1-5 -alkoxide, nitro and halo-C 1-5 -alkyl and said C 1-5 -alkyl being optionally substituted by phenyl; and the ketone has the structure (R 2 ) 2 CO, where R 2 is selected from cyclic-C 3-6 -alkyl.

4. The process as claimed in claim 1 , wherein said amine is a secondary amine of the structure R 3 R 4 NH, where R 3 and R 4 are independently selected from C 1-5 -alkyl; or wherein said amine is a heterocyclic secondary amine having 5 to 6 ring atoms.

5. The process as claimed in claim 1 , wherein said reacting step is undertaken at a temperature from 50° C. to 150° C.

6. A process for producing a 1,2,3-triazole comprising the steps of:
(a) reacting a metal acetylide, a primary or secondary amine and a ketone or an aldehyde in the presence of a transition metal catalyst to form an aminopropyne intermediate compound; and
(b) adding sodium azide and any one of an aryl substituted with a halo group or a halo-C 1-5 -alkane to said aminopropyne intermediate compound of step (a) to produce the 1,2,3-triazole;
wherein:
the metal acetylide is selected from the group consisting of calcium carbide (CaC 2 ), lithium acetylide (Li 2 C 2 ) and lanthanium acetylide (LaC 2 ); and
the transition metal of said transition metal catalyst is selected from the group consisting of copper, silver and gold; wherein when the transition metal is copper, the transition metal catalyst is selected from the group consisting of copper chloride, copper bromide, copper iodide, copper fluoride, copper acetate and copper acetylacetonate.

7. A process for producing an enaminone comprising the step of reacting a metal acetylide, an amine and an aldehyde in the presence of a transition metal catalyst;
wherein:
the metal acetylide is selected from the group consisting of calcium carbide (CaC 2 ), lithium acetylide (Li 2 C 2 ) and lanthanium acetylide (LaC 2 );
the transition metal of said transition metal catalyst is selected from the group consisting of copper, silver and gold; wherein when the transition metal is copper, the transition metal catalyst is selected from the group consisting of copper chloride, copper bromide, copper iodide, copper fluoride, copper acetate and copper acetylacetonate; and
wherein said amine is a secondary amine of the structure R 5 R 6 NH, where R 5 and R 6 is independently selected from C 1-5 -alkyl and cyclo-C 3-6 -alkyl; or wherein said amine is a heterocyclic secondary amine having 5 to 6 ring atoms.

8. The process as claimed in claim 7 , wherein said aldehyde has the structure R 1′ CHO, where R 1′ is selected from aryl, said aryl being optionally substituted by at least one of halide, nitrile, C 1-5 -alkyl, C 1-5 -alkoxide, nitro and halo-C 1-5 -alkyl.

9. The process as claimed in claim 7 , comprising the step of adding a solvent to said reacting step, said solvent being selected to induce formation of said enaminone.

10. The process as claimed in claim 9 , wherein said solvent is a formamide or a sulphoxide.

Assignees

• Zhang Yugen
• Yu Dingyi
• Lin Zhewang
• Agency Science Tech & Res

Inventors

• Zhang Yugen
• Yu Dingyi
• Lin Zhewang

Classifications

• C07C211/29

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title

• C07B37/02

  Addition · CPC title

• C07C211/27

  having amino groups linked to the six-membered aromatic ring by saturated carbon chains · CPC title

• C07C255/58

  containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton · CPC title

• C07C211/35

  containing only non-condensed rings · CPC title