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US 2018/0273450 A1Published application
Process for the preparation of organic bromides
AssigneeTechnion Research & Development Foundation Limited
InventorsMark GANDELMAN, Gennady NISNEVICH, Kseniya KULBITSKI, Alexander ARTARYAN
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Abstract
The present invention provides a process for the preparation of organic bromides, by a radical bromodecarboxylation of carboxylic acids with a bromoisocyanurate.
Claims43
A process for the preparation of organic bromide of formula (1A) from a carboxylic acid of formula (2A) represented by scheme 1:
- said process comprises radical bromodecarboxylation reaction of carboxylic acid (2A) with a bromoisocyanurate to yield organic bromide (1A);
- wherein
- said bromoisocyanurate is tribromoisocyanuric acid, dibromoisocyanuric acid, bromodichloroisocyanuric acid, dibromochloroisocyanuric acid, bromochloroisocyanuric acid, or any combination thereof;
- A is arene, alkane, cycloalkane or saturated heterocycle;
- n is an integer of at least 1;
- m is an integer of at least 0;
- and
- each Q is independently F, Cl, Br, R1, acyl, C(O)R1, C(O)OR1, C(O)Cl, C(O)N(R1)2, CN, SO2R1, SO3R1, NO2, N(R1)3+, OR1, OCF3, O-acyl, OC(O)R1, OSO2R1, SR1, S-acyl, SC(O)R1, N(R1)acyl, N(R1)C(O)R1, N(R1)SO2R1, N(acyl)2, N[C(O)R1]SO2R1, N[C(O)R1]2, CF3;
- or any two vicinal Q substituents are joined to form a 5- or 6-membered substituted or unsubstituted, saturated or unsaturated carbocyclic or heterocyclic ring;
- wherein each R1 is independently aryl, alkyl, cycloalkyl or heterocyclyl, wherein said R1 is optionally substituted by one or more substituents of R2;
- wherein each R2 is independently F, Cl, Br, COOH, acyl, aryl, alkyl, cycloalkyl or heterocyclyl;
- wherein if either one of R2 in (2A) is carboxylic group COOH, then the respective R2 in (1A) is Br;
- wherein the position of said Br and Q in said structure of formula (1A) correspond to the same position of said COOH and Q, respectively in said structure of formula (2A).
10 more elements
(canceled)
13-16. (canceled)
21-23. (canceled)
25-27. (canceled)
A radiation-sensitive composition comprising carboxylic acid of formula (2A)
- and bromoisocyanurate which generates organic bromide of formula (1A)
- upon electromagnetic irradiation,
- wherein
- the bromoisocyanurate is tribromoisocyanuric acid, dibromoisocyanuric acid, bromodichloroisocyanuric acid, dibromochloroisocyanuric acid, bromochloroisocyanuric acid, or any combination thereof;
- A is arene, alkane, cycloalkane or saturated heterocycle;
- n is an integer of at least 1;
- m is an integer of at least 0;
- each Q is independently F, Cl, Br, R1, acyl, C(O)R1, C(O)OR1, C(O)OMe, C(O)Cl, C(O)N(R1)2, CN, SO2R1, SO3R1, NO2, N(R1)3+, OR1, OCF3, O-acyl, OC(O)R1, OSO2R1, SR1, S-acyl, SC(O)R1, N(R1)acyl, N(R1)C(O)R1, N(R1)SO2R1, N(acyl)2, N[C(O)R1]SO2R1, N[C(O)R1]2, CF3;
- or any two vicinal Q substituents are joined to form a 5- or 6-membered substituted or unsubstituted, saturated or unsaturated carbocyclic or heterocyclic ring;
- wherein each R1 is independently aryl, alkyl, cycloalkyl or heterocyclyl, wherein R1 is optionally substituted by one or more substituents of R2;
- wherein each R2 is independently F, Cl, Br, COOH, acyl, aryl, alkyl, cycloalkyl or heterocyclyl;
- wherein if either one of R2 in (2A) is a carboxylic group COOH, then the respective R2 in (1A) is Br;
- wherein the position of said Br and Q in said structure of formula (1A) correspond to the same position of said COOH and Q, respectively in said structure of formula (2A).
10 more elements
(canceled)
49-54. (canceled)
Dependencies are inferred from the claim text.