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US 10,899,687 B2Granted
Process for the preparation of organic halides
AssigneeTechnion Research & Development Foundation Limited
InventorsMark Gandelman, Gennady Nisnevich, Kseniya Kulbitski, Alexander Artaryan
Life of this patent
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Abstract
The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.
Claims28
A process for the preparation of at least one organic halide of formula (1A) from a carboxylic acid of formula (2A) represented by scheme 1:
- said process comprises radical halo-de-carboxylation reaction comprising reacting carboxylic acid (2A) with a chloroisocyanurate and a brominating agent to yield organic halide (1A);
- wherein
- said chloroisocyanurate is trichloroisocyanuric acid, dichloroisocyanuric acid, or any combination thereof;
- A is arene, alkane, cycloalkane or saturated heterocycle;
- n is an integer greater than or equal to 1;
- X is Cl or Br;
- wherein if n>1, then X may be the same or different;
- k is an integer greater than or equal to 0;
- Y is Cl or Br;
- wherein if k>1, then Y may be the same or different;
- m is an integer greater than or equal to 0;
- 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 or Cl;
- wherein the position of said X, Y and Q in said structure of formula (1A) correspond to the same position of said COOH, Br and Q, respectively in said structure of formula (2A).
14 more elements
A radiation-sensitive composition comprising a carboxylic acid (2A)
- a chloroisocyanurate and a brominating agent which generates organic halide (1A)
- upon electromagnetic irradiation,
- wherein
- said chloroisocyanurate is trichloroisocyanuric acid, dichloroisocyanuric acid, or any combination thereof;
- A is arene, branched alkane, cycloalkane or saturated heterocycle;
- n is an integer greater than or equal to 1;
- X is Cl or Br;
- wherein if n>1, then X may be the same or different;
- k is an integer greater than or equal to 0;
- Y is Cl or Br;
- wherein if k>1, then Y may be the same or different;
- m is an integer greater than or equal to 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)R, 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 or Cl;
- 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).
15 more elements
Dependencies are inferred from the claim text.