Nitration

Patent metadata

Field	Value
Publication number	US-11655203-B2
Application number	US-201917288819-A
Country	US
Kind code	B2
Filing date	Oct 24, 2019
Priority date	Oct 26, 2018
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

A process for preparing a nitrated compound, including the step of reacting a compound (A) including at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein the heteroaromatic ring includes at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I)wherein Y is selected from the group consisting of hydrogen and nitro.

First claim

The invention claimed is:

1. A process for preparing a nitrated compound, comprising the step of
reacting a compound (A) having at least one aromatic or heteroaromatic ring optionally substituted by one or more organic residues R,
wherein the organic residue R is selected from the group consisting of fluoro, chloro, bromo, iodo, amino, cyano, hydroxy, nitro, C 1-12 alkyl, C 2-15 alkenyl, C 2-15 alkynyl, C 3-15 cycloalkyl, C 3-15 cycloalkenyl, cycloalkynyl, C 3-5 alkylene, C 3-5 cycloalkylene, C 3-5 alkenylene, C 3-5 alkynylene, halo-C 1-6 alkyl, hydroxy-C 1-6 alkyl, halo-C 3-15 cycloalkyl, C 1-10 alkoxy, C 3-5 cycloalkoxy, alkylenedioxy, C 1-6 acyl, C 3-6 cycloacyl, C 1-6 acyloxy, C 3-6 cycloacyloxy, arylalkyl, heteroarylalkyl, aryl, and heteroaryl group, and where the organic residue R may optionally form an annealed ring system with other rings selected from cycloalkyl, aryl, and heteroaryl rings, and
wherein the heteroaromatic ring includes at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen,

with a compound of formula (I)

wherein Y is selected from the group consisting of hydrogen and nitro.

2. The process according to claim 1 , wherein compound (A) includes at least one acid-sensitive residue.

3. The process according to claim 1 , wherein the aromatic ring or the heteroaromatic ring of compound (A) includes at least one electron donating group as residue.

4. The process according to claim 1 , wherein the aromatic ring or the heteroaromatic ring of compound A includes at least one electron withdrawing group as residue.

5. The process according to claim 1 , wherein the compound (A) includes or is a 5- or 6-membered aromatic or heteroaromatic ring optionally substituted by one or more organic residues R, wherein the organic residue R is selected from the group consisting of fluoro, chloro, bromo, iodo, amino, cyano, hydroxy, nitro, C 1-12 alkyl, C 2-15 alkenyl, C 2-15 alkynyl, C 3-15 cycloalkyl, C 3-15 cycloalkenyl, cycloalkynyl, C 3-5 alkylene, C 3-5 cycloalkylene, C 3-5 alkenylene, C 3-5 alkynylene, halo-C 1-6 alkyl, hydroxy-C 1-6 alkyl, halo-C 3-15 cycloalkyl, C 1-10 alkoxy, C 3-5 cycloalkoxy, alkylenedioxy, C 1-6 acyl, C 3-6 cycloacyl, C 1-6 acyloxy, C 3-6 cycloacyloxy, arylalkyl, heteroarylalkyl, aryl, and heteroaryl group, and where the organic residue R may optionally form an annealed ring system with other rings selected from cycloalkyl, aryl, and heteroaryl rings.

6. The process according to claim 1 , wherein the compound (A) includes or is a fused aromatic or heteroaromatic ring system having 2 to 5 aromatic or heteroaromatic rings which may be optionally substituted by one or more organic residues R, wherein the organic residue R is selected from the group consisting of fluoro, chloro, bromo, iodo, amino, cyano, hydroxy, nitro C 1-12 alkyl, C 2-15 alkenyl, C 2-15 alkynyl, C 3-15 cycloalkyl, C 3-15 cycloalkenyl, cycloalkynyl, C 3-5 alkylene, C 3-5 cycloalkylene, C 3-5 alkenylene, C 3-5 alkynylene, halo-C 1-6 alkyl, hydroxy-C 1-6 alkyl, halo-C 3-15 cycloalkyl, C 1-10 alkoxy, C 3-5 cycloalkoxy, alkylenedioxy, C 1-6 acyl, C 3-6 cycloacyl, C 1-6 acyloxy, C 3-6 cycloacyloxy, arylalkyl, heteroarylalkyl, aryl, and heteroaryl group, and where the organic residue R may optionally form an annealed ring system with other rings selected from cycloalkyl, aryl, and heteroaryl rings.

7. The process according to claim 1 , wherein the heteroaromatic ring or ring system is selected from the group consisting of pyrrole, thiophene, furan, imidazole, thiazole, pyrimidine, pyridine, pyrazine, pyridazine, isoxazole, oxazole, indole, isoindole, indolizine, quinoline, isoquinoline, purine, carbazole, dibenzofuran, acridine, purine, guanine, xanthine, uric acid, benzothiophen, benzofuran, dibenzothiophen, thianthren, xanthen, phenoxatiin, isochinoline, phthalazine, 1,8-naphthydrine, quinazoline, quinoxaline, cinnoline, pteridine, perimidine, 1,7-phenanthroline, phenazine, phosphindole, phthalimide, furazan and phosphinoline.

8. The process according to claim 1 , wherein the aromatic ring or ring system is selected from the group consisting of benzene, pentalene, indene, indan, naphthalene, 1,1′-binaphthalene, azulene, heptalene, biphenylene, as-indacene, s-indacene, acenaphthylene, fluorene phenalene, phenanthrene, anthracene, fluoranthene acephenanthrylene, aceanthrylenetriphenylene, pyrene chrysene, naphthacene, pleiadene, picene and perylene.

9. The process according to claim 1 , wherein the compound of formula (I) is the compound of formula (Ia)

10. The process according to claim 1 , wherein the compound of formula (I) is the compound of formula (Ib)

11. The process according to claim 1 , wherein the reaction is carried out in a solvent selected from the group consisting of hexafluoroisopropanol, acetonitrile, nitromethane, methylenechloride, trifluoroethanol, tetrahydrofuran, hexane, benzene, toluene, and mixtures thereof.

12. The process according to claim 1 , wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of acetic acid, trimethylacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, iron (II) triflate, iron (III) triflate, magnesium (II) triflate, zinc (II) triflate, cupper (II) triflate, iron (II) bromide, iron (III) bromide, magnesium perchlorate, and mixtures thereof.

13. The process according to claim 12 , wherein the catalyst is selected from the group consisting of acetic acid, trimethylacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, and mixtures thereof.

14. The process according to claim 12 , wherein the catalyst is selected from the group consisting of iron (II) triflate, iron Me triflate, magnesium (II) triflate, zinc (II) triflate, cupper (II) triflate, iron (II) bromide, iron (III) bromide and magnesium perchlorate.

15. A method comprising applying a compound of formula (I)

wherein Y is selected from the group consisting of hydrogen and nitro,
as nitrating agent of a compound (A) comprising an aromatic or heteroaromatic ring.

16. The process according to claim 2 , wherein the acid-sensitive residue is selected from the group consisting of difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, chloro, iodo, methoxy, ethoxy, propoxy, butoxy, amino, methylamino, dimethylamino, formyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acyl chlorides, acid anhydrides, carboxylate esters, sulfonate esters, alkyl esters, carboxy, ketals, acetals, hydrazones carboxy, and 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl.

17. The process according to claim 3 , wherein the electron donating group is selected from the group consisting of amino, carbamoyl, alkylaminocarbonyl, carboxamido, mercapto, alkylthio, hydroxy, alkoxy, alkyl, acyloxy, aryl, heteroaryl, alkenyl, and alkynyl.

18. The process according to claim 4 , wherein the electron withdrawing group is selected from the group consisting of fluoro, chloro, bromo, iodo, acyl, carboxy, benzoyl, carbonyl, aldehyde, arylsulfonyl, haloalkyl, cyano, and 2,5-dioxopyrrolidinyl.

Assignees

• Eth Zuerich

Inventors

• Katayev Dmitry
• Zhang Kun
• Calvo Roxan

Classifications

• C07D311/72

  3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols · CPC title

• C07D233/92

  attached in position 4 or 5 · CPC title

• C07C2602/08

  the other ring being five-membered, e.g. indane · CPC title

• C07C2601/02

  with a three-membered ring · CPC title

• C07D239/30

  Halogen atoms or nitro radicals · CPC title