Method for the preparation of iodoalkanes

Patent metadata

Field	Value
Publication number	US-10040740-B2
Application number	US-201715406029-A
Country	US
Kind code	B2
Filing date	Jan 13, 2017
Priority date	Jan 14, 2016
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

The present invention relates to an atom economic procedure of preparing iodoalkanes by hydroiodination of alkenes. In particular the present method features the generation of anhydrous hydrogen iodide from atomic hydrogen and iodine in situ by using transition metal precursor and phosphine ligandcatalyst.

First claim

The invention claimed is:

1. A method of producing iodoalkanes comprising hydroiodinating alkene with hydrogen and iodine with a transition metal precursor and a phosphine ligand as catalyst, wherein said metal precursor is selected from the group consisting of a Rh(COD) 2 BF 4 , Rh(CO) 2 (C 5 H 7 O 2 ), [Rh(COD)Cl] 2 , Rh(COD) 2 SbF 6 , Rh(COD) 2 OTf, C 14 H 16 Cl 2 Rh 2 , [Ir(COD)Cl] 2 , and Ru(COD)Cl 2 .

2. The method according to claim 1 , further comprising converting the hydrogen and iodine into anhydrous hydrogen iodide.

3. The method according to claim 1 wherein said hydroiodinating step is performed in situ and the hydrogen and iodine are atomic hydrogen and iodine.

4. The method according to claim 1 wherein the phosphine ligand is selected from the group consisting of (±)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl ((±)-Binap), triphenylphosphine (PPH 3 ), ethylenebis(diphenylphosphine) (DPPE), 1,4-bis(diphenylphosphino)butane (DPPB), 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (XANTPHOS), 1,1′-Ferrocenediyl-bis(diphenylphosphine) (DPPF), and tricyclohexyphosphine.

5. The method according to claim 1 wherein the method is performed under a pressure of 2-6 Mpa and at 0-40° C.

6. The method according to claim 1 wherein the alkene, transition metal precursor and phosphine ligand are dissolved in a solvent.

7. The method according to claim 6 wherein the solvent is selected from the group consisting of dichloroethane (DCE), toluene, and dichloromethane (DCM).

8. The method according to claim 1 , wherein the hydroiodinating step is

9. The method according to claim 1 , wherein the hydroiodinating step is

wherein R is phenyl, 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-methylphenyl, 2,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-methoxyphenyl, 4-phenylbenzene, cyclohexyl, n-hexyl, n-dodecyl, benzyl, or phenethyl.

10. The method according to claim 1 , wherein the hydroiodinating step comprises
mixing the transition metal precursor, the phosphine ligand, a solvent to produce a first solution;
stirring the first solution at room temperature to produce a second solution;
adding iodine and alkene to the second solution to produce a reaction mixture;
autoclaving the reaction mixture;
stirring the reaction mixture at room temperature under a pressure of 4 Mpa;
removing the solvent to produce a residue; and
purifying the residue to obtain the iodoalkane.

11. The method according to claim 1 , wherein the ratio of alkene to iodine to transition metal precursor to phosphine ligand is 1:1:0.05:0.065.

12. The method according to claim 1 , wherein the transition metal precursor is 0.01%-5% of the reaction mixture and the phosphine ligand is 0.01%-6% of the reaction mixture.

13. The method according to claim 11 , wherein the reaction mixture is stirred for 6 to 96 hours.

14. The method according to claim 5 , wherein method is performed under a pressure of 4 Mpa and at 20-25° C.

Assignees

• Univ Hong Kong Baptist Univ
• Univ Yunnan Minzu

Inventors

• Bian Zhaoxiang
• Fan Baomin
• Lin Chengyuan
• Zhou Yongyun
• Chen Jingchao

Classifications

• C07C17/04

  to unsaturated halogenated hydrocarbons · CPC title

• C07C17/08

  to unsaturated hydrocarbons · CPC title

• C07C41/22 Primary

  by introduction of halogens; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C17/087

  to unsaturated halogenated hydrocarbons · CPC title

• C07C17/02

  to unsaturated hydrocarbons · CPC title