Sulfamic acid derivatives and processes for their preparation

Patent metadata

Field	Value
Publication number	US-2020181071-A1
Application number	US-201716343324-A
Country	US
Kind code	A1
Filing date	Oct 19, 2017
Priority date	Oct 19, 2016
Publication date	Jun 11, 2020
Grant date	—

Abstract

Here are described processes for the preparation of sulfamic acid derivatives, for instance, halogenated derivatives and their metallic or organic salts. The present document also describes the sulfamic acid derivatives thus produced and to their uses, for instance, in electrolyte compositions for electrochemical applications.

First claim

1 . A process for the preparation of a sulfamic acid derivative of Formula I:

wherein,
R 1 is selected from the group consisting of a hydrogen atom and linear or branched C 1 -C 24 alkyl, C 6 -C 10 aryl and C 5 -C 10 heteroaryl groups, said groups being optionally halogenated, or R 1 and the adjacent nitrogen atom together form a salt wherein the nitrogen atom is negatively charged (anion) and R 1 is (M n+ ) 1/n or X + ;
R 2 is selected from the group consisting of a hydrogen atom and the groups cyano, sulfonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, optionally halogenated linear or branched C 1 -C 24 alkanoyl, optionally halogenated C 6 -C 10 aryloyl, optionally halogenated C 5 -C 10 heteroaryloyl, optionally halogenated linear or branched C 1 -C 24 -alkanesulfonyl, optionally halogenated C 6 -C 10 arylsulfonyl, and optionally halogenated C 5 -C 10 heteroarylsulfonyl;
R 3 is selected from the group consisting of OH, F, Cl, O − (M n+ ) 1/n , O − X + , and optionally halogenated linear or branched C 1 -C 24 alkoxy;
(M n+ ) 1/n is a metal cation, wherein M is a metal and n is an integer selected from the range of 1 to 4, for instance, M is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Sc, Y, Fe, Co, Ni, Ti, Sn, V, Cr, or Mn, for example, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Sc, and Ti, for instance is an alkali metal, alkaline earth metal, or aluminum, or M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and n is 1 or 2; and
X + represents an organic cation, for instance, selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium, and the like;
the process comprising the steps of:
i) contacting a compound of the formula:

with a sulfur trioxide source and a tertiary amine and heating at a temperature comprised between about 50° C. and about 300° C., between about 100° C. and about 250° C., or between about 150° C. and about 220° C., preferably for a period of less than 10 hours, less than 4 hours, or less than 1 hour; and
ii) optionally converting the product obtained in step (i) to produce a compound of Formula I.

2 . The process of claim 1 , wherein the sulfur trioxide source is selected from SO 3 (sulfur trioxide) and its oligomers and polymers; H 2 SO 4 (sulfuric acid); H 2 S 2 O 7 (disulfuric acid) and other polysulfuric acids and their salts; ClSO 3 H (chlorosulfonic acid) and its salts; FSO 3 H (fluorosulfonic acid) and its salts; SO 3 -ammonia complex (sulfamic acid); complexes of sulfur trioxide with organic amines; complexes of sulfur trioxide with other organic compounds such as dioxane, thioxane, dimethylformamide; and acylsulfates which are generated by SO 3 introduction into dry carboxylic acids, for example, acetyl sulfate (CH 3 C(O)OSO 3 H).

3 . The process of claim 1 , wherein the sulfur trioxide source and the tertiary amine are added together as a complex, and the tertiary amine is selected from trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, N-alkyl substituted pyrrolidines and morpholines, pyridine, picoline, lutidine, quinoline, N,N-dimethylaniline, and other amines, for example the complex is selected from pyridine-sulfur trioxide, trimethylamine-sulfur trioxide and triethylamine-sulfur trioxide complexes.

4 - 6 . (canceled)

7 . The process of claim 1 , wherein step (i) is carried out without addition of solvent.

8 . The process of claim 1 , the process comprising step (ii) which comprises contacting the product obtained in step (i) with a metallic base, for example selected from metal hydroxides, metal alkoxides, organometallics and Grignard reagents, said metal being selected from alkali metals, alkaline earth metals, and aluminium, preferably, the metallic base is a metal hydroxide.

9 . (canceled)

10 . (canceled)

11 . The process of claim 1 , further comprising a step of treating the product of step (i) or of step (ii) with a strong acid or contacting a solution thereof with an acidic ion exchange resin, for example, the strong acid is selected from hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and trifluoromethanesulfonic acid.

12 . (canceled)

13 . The process of claim 1 , the process comprising step (ii) which comprises contacting the product obtained in step (i) with a chlorinating agent, for example, the chlorinating agent is selected from inorganic and organic acid chlorides such as PCl 5 , POCl 3 , SOCl 2 , ClSO 3 H, COCl 2 , ClCOCOCl, sulfur chlorides, cyanuric chloride, acetyl chloride, trifluoroacetyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzoyl chloride, (trichloromethyl)benzene, benzenesulfonyl chloride, and toluenesulfonyl chloride, preferably the chlorinating agent is SOCl 2 , COCl 2 , or ClCOCOCl.

14 . (canceled)

15 . (canceled)

16 . The process of claim 13 , further comprising, in step (ii), contacting the product obtained with a fluorinating agent after contacting with the chlorinating agent.

17 . The process of claim 16 , wherein the fluorinating agent is selected from hydrogen fluoride, fluoride or hydrogen difluoride salts (like ammonium, sodium, potassium, or cesium fluoride or hydrogen difluoride), and a complex salt of amines and hydrofluoric acid (such as pyridinium or triethylammonium polyhydrofluorides), preferably the fluorinating agent is KF or KHF 2 .

18 . (canceled)

19 . The process of claim 1 , wherein the process comprises step (ii) which comprises contacting the product obtained in step (i) with a fluorinating agent.

20 . The process of claim 19 , wherein said fluorinating agent is selected from reactive inorganic and organic acid fluorides, such as PF 5 , POF 3 , SOF 2 , FSO 3 H, COF 2 , FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and its organic derivatives (like diethylaminosulfur trifluoride (DAST) and morpholinosulfur trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride, (trifluoromethyl)benzene, benzenesulfonyl fluoride, and toluenesulfonyl fluoride.

21 . (canceled)

22 . A sulfamic acid derivative defined according to Formula I, II or III:

wherein,
R 1 is selected from the group consisting of a hydrogen atom and linear or branched C 1 -C 24 alkyl, C 6 -C 10 aryl and C 5 -C 10 heteroaryl groups, said groups being optionally halogenated, or R 1 and the adjacent nitrogen atom together form a salt wherein the nitrogen atom is negatively charged (anion) and R 1 is (M n+ ) 1/n , or X + ;
R 2 is selected from the group consisting of a hydrogen atom and a cyano, sulfonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, optionally halogenated linear or branched C 1 -C 24 alkanoyl, optionally halogenated C 6 -C 10 aryloyl, optionally halogenated C 5 -C 10 heteroaryloyl, optionally halogenated linear or branched C 1 -C 24 alkanesulfonyl, optionally halogenated C 6 -C 10 arylsulfonyl, or optionally halogenated C 5 -C

Assignees

• Hydro Quebec

Inventors

• Kozelj Matjaz
• Gagnon Catherine
• Guerfi Abdelbast
• Zaghib Karim

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• Y02T10/70

  Energy storage systems for electromobility, e.g. batteries · CPC title

• H01G11/62

  characterised by the solute, e.g. salts, anions or cations therein · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• C07C303/40 Primary

  by reactions not involving the formation of sulfonamide groups · CPC title