JPWO2020202131A5

JPWO2020202131A5 -

Info

Publication number: JPWO2020202131A5
Application number: JP2021556704A
Authority: JP
Publication date: 2023-02-20

Claims

A method for obtaining a salt having the general formula R _x NI, comprising:
- R _x N is an organic cation (R _x N ⁺ );
R represents a substituent (R-) independently selected from the group consisting of organic substituents R ¹ -, R ² -, R ³ -, and hydrogen (H-), and the organic cation R _x N ⁺ The donor of has the general formula C _y H _z containing 1 to 8 carbon atoms in the substituted molecule and optionally containing at least one heteroatom replacing a carbon or hydrogen atom in the substituted molecule contains as organic substituents R ¹ -, R ² -, and optionally R ³ - moieties independently selected from the group consisting of straight or branched chain alkyl substituents having , oxygen , nitrogen, sulfur, iodine, chlorine, and bromine;
- x is the number of the substituents R- directly bonded to the nitrogen (N) atom in the organic cation R _x N ⁺ , x is 3 or 4;
-I is an iodide anion (I ^- ),
The method includes
- in situ iodination by mixing molecular iodine (I ₂ ) and formic acid (COOH) in a solvent medium at a molecular iodine (I ₂ ):formic acid (COOH) molar ratio of 1.01:1 or greater; synthesizing hydrogen (HI);
- introducing into said solvent medium a compound which is a donor of said organic cation R _x N ⁺ in an amount which gives a molar ratio of donor of said organic cation R _x N ⁺ : molecular iodine (I ₂ ) of 1.01:1 or more. and
- maintaining the reaction mixture at a temperature of 20°C or higher for the time required to obtain the reaction product, which is said salt having the general formula R _x NI ,
Amines are used as donors for the organic cations R _x N ⁺ and the resulting salts (R _x NI) are alkylammonium cations (R(H ₃ )N ⁺ ), dialkylammonium cations R ₂ (H ₂ )N ⁺ and the organic cation (R _x N ⁺ ) selected from the group consisting of trialkylammonium cations ( R ₃ (H) N ⁺ );
Alternatively, formamidine acetate is used as a donor of said organic cation R _x N ⁺ to obtain formamidinium iodide (FAI) (H ₂ N—C(H)=N(H ₂ )I) ,
Method.

Molecular iodine (I ₂ ) is mixed with formic acid (HCOOH) in a molar ratio of iodine molecule (I ₂ ):formic acid (COOH) of 1.01:1 to 1.1:1 to form the organic cation R _x N ⁺ is introduced into the solvent medium in an amount to give a molar ratio of donor of the organic cation R _x N ⁺ to molecular iodine (I ₂ ) of 1.01:1 to 1.50:1 ; A cation R _x N ⁺ donor is introduced into the solvent medium following in situ synthesis of hydrogen iodide (HI) and the prepared reaction mixture is heated to a temperature in the range of 20-80°C. The method of claim 1, wherein :

the organic cation R _x N ⁺ donor used is selected from the group consisting of methylamine to obtain methylammonium iodide (MAI) or octylamine to obtain octylammonium iodide (OAI), 3. A method according to claim 1 or 2 .

The medium of claims 1 to 3 , wherein the solvent medium contains at least one compound selected from the group consisting of methanol, ethanol, absolute ethanol, isopropanol, dioxane, tetrahydrofuran (THF) , dimethylformamide (DMF) and water. A method according to any one of paragraphs.

5. Any one of claims 1 to 4 , wherein the step of preparing a reaction mixture further comprises introducing into the solvent medium a catalyst that is the same compound as the salt R _x NI that is the reaction product. The method described in .

Process according to claim 5 , wherein the catalyst is obtained by the process according to any one of claims 1-4 .

A process according to claim 5 or 6 , wherein the catalyst is introduced in a molar ratio of catalyst: molecular iodine (I ₂ ) ranging from 0.01:1 to 0.03:1.