N-transfer reagent and method for preparing the same and its application

Patent metadata

Field	Value
Publication number	US-11040939-B1
Application number	US-202017010499-A
Country	US
Kind code	B1
Filing date	Sep 2, 2020
Priority date	Jun 23, 2020
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

The various novel N-transfer reagents of the present invention can be quickly prepared by employing different nitrobenzene precursors. The N-transfer reagents can directly convert a variety of amino compounds into diazo compounds under mild conditions. Particularly, the N-transfer reagents can facilitate the synthesis of the diazo compounds. The application of synthesizing diazo compounds of the present invention can greatly decrease the difficulty in operation, increase the safety during experiments, reduce the cost of production and the environmental pollution, and enhance the industrial value of diazo compounds.

First claim

What is claimed is:

1. An N-transfer reagent represented by the following Formula (I):

wherein n1 is an integer from 0 to 5, and R 1 is selected from the group consisting of: a deuterium atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aldehyde group having 1 to 12 carbon atoms, a ketone group having 2 to 12 carbon atoms, an ester group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a sulfonic acid group, a sulfonyl group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms;
wherein n2 is an integer from 0 to 4, and R 2 is selected from the group consisting of: a deuterium atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aldehyde group having 1 to 12 carbon atoms, a ketone group having 2 to 12 carbon atoms, an ester group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a polyether group having 3 to 12 carbon atoms, a sulfonic acid group, a sulfonyl group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms; or when n2 is 2, the two (R 2 )s are adjacent and connect with each other to form a 1,3-dioxolane group or a 1,4-dioxane group;
wherein R 3 and R 4 are each independently selected from the group consisting of; a hydrogen atom, a deuterium atom, and an alkyl group having 1 to 6 carbon atoms;
wherein X − is selected from the group consisting of: a hexafluorophosphate anion, a tetrafluoroborate anion, a halogen anion, and a p-toluenesulfonate anion; and
wherein m is an integer from 0 to 3.

2. The N-transfer reagent as claimed in claim 1 , wherein m is 1.

3. The N-transfer reagent as claimed in claim 1 , wherein R 3 is the hydrogen atom, and R 4 is the hydrogen atom.

4. The N-transfer reagent as claimed in claim 1 , wherein X − is the hexafluorophosphate anion.

5. The N-transfer reagent as claimed in claim 1 , wherein n1 is an integer from 1 to 4, and R 1 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, or an acetyl group.

6. The N-transfer reagent as claimed in claim 1 , wherein n1 is an integer from 1 to 3, and R 1 is a methyl group, an ethyl group, a propyl group, or a butyl group.

7. The N-transfer reagent as claimed in claim 1 , wherein n2 is an integer from 1 to 3, and each R 2 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a methyl ester group, an acetoxy group, an ethylene oxide methyl ether group, a diethylene oxide methyl ether group, or a triethylene oxide ethyl ether group; or n2 is the integer 2, and the two (R 2 )s are adjacent and connect with each other to form the 1,3-dioxolane group.

8. The N-transfer reagent as claimed in claim 1 , wherein the N-transfer reagent is selected from the group consisting of the following:

9. A method for producing the N-transfer reagent as claimed in claim 1 , comprising the following steps:
step (A): reacting a nitrobenzene precursor represented by the following Formula (II) with a metal catalyst in an atmosphere containing a hydrogen gas to obtain an aniline compound,

wherein n1 is an integer from 0 to 5, and R 1 is selected from the group consisting of: a deuterium atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aldehyde group having 1 to 12 carbon atoms, a ketone group having 2 to 12 carbon atoms, an ester group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a sulfonic acid group, a sulfonyl group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms;
wherein n2 is an integer from 0 to 4, and R 2 is selected from the group consisting of: a deuterium atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aldehyde group having 1 to 12 carbon atoms, a ketone group having 2 to 12 carbon atoms, an ester group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a polyether group having 3 to 12 carbon atoms, a sulfonic acid group, a sulfonyl group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms; or when n2 is 2, the two (R 2 )s are adjacent and connect with each other to form a 1,3-dioxolane group or a 1,4-dioxane group;
wherein R 3 and R 4 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, and an alkyl group having 1 to 6 carbon atoms; and
wherein m is an integer from 0 to 3; and
step (B): reacting the aniline compound with a nitrosonium ion to undergo diazotization so as to obtain the N-transfer reagent.

10. The method as claimed in claim 9 , wherein the step (B) further comprises:
step (b1): reacting the aniline compound with the nitrosonium ion to undergo diazotization so as to obtain a mixture; and
step (b2): purifying the mixture by concentrating, recrystallizing, or a sedimentation method to obtain the N-transfer reagent.

11. The method as claimed in claim 9 , wherein the method is performed at a temperature from −15° C. to 25° C.

12. The method as claimed in claim 9 , wherein the amount of the metal catalyst is 5% to 20% of the weight of the nitrobenzene precursor.

13. The method as claimed in claim 9 , wherein the metal catalyst comprises palladium on carbon, a platinum metal, a tin metal, a rubidium metal, a rhodium metal, a ruthenium metal, or an iridium metal.

14. An application of the N-transfer reagent as claimed in claim 1 , wherein the application comprises: reacting an amino compound and the N-transfer reagent as claimed in claim 1 with a basic reagent in a solvent to convert the amino compound into a diazo compound.

15. The application as claimed in claim 14 , wherein the application is performed at a temperature from −10° C. to 50° C.

16. The application as claimed in claim 14 , wherein the basic reagent comprises potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, triethylamine, N, N-diisopropylethylamine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, or 1,8-diazabicyclo[5.4.0]undec-7-ene.

17. The application as claimed in claim 14 , wherein the amino compound comprises an α-amino ketone, an α-amino amide, an α-amino ester, or an α-amino phosphonate ester.

18. The application as claimed in claim 14 , wherein the diazo compound is selected from the group consisting of the following:

Assignees

• Univ Nat Cheng Kung

Inventors

• Chou Ho-Hsuan
• Lu Guan-Han
• Hsueh Hsiao-Chin
• Huang Tzu-Chia

Classifications

• C07F9/4015

  Esters of acyclic unsaturated acids · CPC title

• C07D317/66

  Nitrogen atoms not forming part of a nitro radical · CPC title

• C07D233/64

  with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine · CPC title

• C07D209/42

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07C323/57

  the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups · CPC title