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US 2022/0380321 A1Published application
Process for the preparation of biphenylamines
AssigneeAdama Makhteshim Ltd.
InventorsXi ZHEN, Pingping TANG, Natali ASHUSH, Einat KISIN-FINFER
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Abstract
The invention relates to a method for the preparation of 2-aminobiphenyls, key intermediates in the preparation of compounds of interest in the agrochemical industry. The process comprises reacting an ortho-substituted aniline and a phenylboro derivative in the presence of a base and a palladium catalyst, said palladium catalyst comprising a palladium source and a biphenyl phosphine ligand of formula (III) or a salt thereof.
Claims39
A process to prepare a compound of formula (IV) or a salt thereof
- wherein
- q is an integer selected from the group consisting of 0, 1, 2, 3 and 4;
- p is an integer selected from the group consisting of 0, 1, 2, 3, 4 and 5;
- provided that at least one of p or q is 1 or more;
- each of R11 and R12 is independently selected from hydrogen and a nitrogen protecting group, or R11 and R12 together form a cyclic nitrogen protecting group;
- each R1 is independently selected from the group consisting of halogen, —OH, C1-C6-alkyl, cyano, C1-C6-haloalkyl, C1-C6-alcoxyl, and C1-C6-haloalcoxyl;
- and
- each R3 is independently selected from the group consisting of halogen, —OH, C1-C6-alkyl, cyano, C1-C6-haloalkyl, C1-C6-alcoxyl and C1-C6-haloalcoxyl;
- the process comprising reacting an ortho-substituted aniline and a phenylboro derivative in the presence of a base and a palladium catalyst, said palladium catalyst comprising a palladium source and a biphenyl phosphine ligand, wherein said ortho-substituted aniline is a compound of formula (I), or a salt thereof
- wherein
- q, R1, R11 and R12 are as defined above;
- and
- X1 is a group capable of transmetalation with palladium;
- wherein said phenylboro derivative is a compound of formula (II)
- wherein
- p and R3 are as defined above;
- y is an integer selected from 0 or 1;
- wherein,
- when y is 1, then z is an integer selected from 1, 2 or 3;
- when y is 0, then z is an integer selected from 1, 2, 3 or 4, and the compound of formula (II) forms a borate accompanied by a cation A having a charge a+;
- and
- each R2 is independently selected from the group consisting of hydrogen, halogen, —OH, —OR9, and C1-C10-alkyl, wherein R9 is C1-C10-alkyl or C6-C12-aryl;
- or wherein, z being 1, two R2 groups together form a bridging group —O—(CH2)r—O—, wherein r is 2 or 3, so that said two R2 groups, together with the oxygen atoms and the boron atom, form a 5- or 6-membered ring, where the CH2 groups are optionally substituted by one or two C1-C4-alkyl groups;
- and
- wherein the biphenyl phosphine ligand is a compound of formula (III) or a salt thereof
- wherein
- m is an integer selected from the group consisting of 0, 1, 2 and 3;
- n is an integer selected from the group consisting of 0, 1, 2, 3 and 4;
- each R4 is independently selected from the group consisting of C1-C16-alkyl, C3-C15-cycloalkyl, and C6-C10-aryl;
- each R5 is independently selected from the group consisting of hydrogen, —OR10, —SR10, —N(R10)(R10), C1-C16-alkyl, C3-C10-cycloalkyl, halogen, cyano, and C1-C6-haloalkyl, provided that one R5 is not hydrogen, wherein R10 is selected from the group consisting of C1-C16-alkyl, C3-C10-cycloalkyl, and C1-C6-haloalkyl;
- each R6 is independently selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxyl and C1-C6-haloalcoxyl;
- each R7 is independently selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxyl and C1-C6-haloalcoxyl.
29 more elements
A process to produce a compound of formula (V), or a salt thereof,
- wherein
- q is an integer selected from the group consisting of 0, 1, 2, 3 and 4;
- p is an integer selected from the group consisting of 0, 1, 2, 3, 4 and 5;
- provided that at least one of p or q is 1 or more;
- R11 is selected from hydrogen or a nitrogen protecting group;
- Q is C6-C15-aryl or C3-C15-heteroaryl, optionally substituted with one or more groups selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl;
- each R1 is independently selected from the group consisting of halogen, —OH, C1-C6-alkyl, cyano, C1-C6-haloalkyl, C1-C6-alcoxyl, and C1-C6-haloalcoxyl;
- and
- each R3 is independently selected from the group consisting of halogen, —OH, C1-C6-alkyl, cyano, C1-C6-haloalkyl, C1-C6-alcoxyl and C1-C6-haloalcoxyl;
- the process comprising the reaction between an ortho-substituted aniline of formula (I), or a salt thereof
- wherein
- q and IV are as defined above;
- and
- X1 is a group capable of transmetalation with palladium;
- R11 is as defined above;
- R12 is selected from hydrogen and a nitrogen protecting group;
- and a phenylboro derivative of formula (II)
- wherein
- p and R3 are as defined above;
- y is an integer selected from 0 or 1;
- wherein,
- when y is 1, then z is an integer selected from 1, 2 or 3;
- when y is 0, then z is an integer selected from 1, 2, 3 or 4, and the compound of formula (II) forms a borate accompanied by a cation A having a charge a+;
- and
- each R2 is independently selected from the group consisting of hydrogen, halogen, —OH, —OR9, and C1-C10-alkyl, wherein R9 is C1-C10-alkyl or C6-C12-aryl;
- or wherein, z being 1, two R2 groups together form a bridging group —O—(CH2)r—O—, wherein r is 2 or 3, so that said two R2 groups, together with the oxygen atoms and the boron atom, form a 5- or 6-membered ring, where the CH2 groups are optionally substituted by one or two C1-C4-alkyl groups;
- in the presence of a base and palladium catalyst, the palladium catalyst comprising a palladium source and a biphenyl phosphine ligand of formula (III) or a salt thereof
- wherein
- m is an integer selected from the group consisting of 0, 1, 2 and 3;
- n is an integer selected from the group consisting of 0, 1, 2, 3 and 4;
- each R4 is independently selected from the group consisting of C1-C16-alkyl, C3-C15-cycloalkyl, C6-C10-aryl;
- each R5 is independently selected from the group consisting of hydrogen, —OR10, —SR10, —N(R10)(R10), C1-C16-alkyl, C3-C10-cycloalkyl, halogen, cyano, and C1-C6-haloalkyl, provided that one R5 is not hydrogen;
- wherein each R10 is independently selected from the group consisting of C1-C16-alkyl, C3-C10-cycloalkyl, C1-C6-haloalkyl, and C1-C6-alcoxyl;
- each R6 is independently selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxyl and C1-C6-haloalcoxyl;
- and
- each R7 is independently selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alcoxyl and C1-C6-haloalcoxyl;
- to provide a compound of formula (IV) or a salt thereof
- wherein
- R1, R3, R11, R12, q, and p are defined above;
- the process further comprising,
- if required, obtaining a compound of formula (IV) wherein at least one of R11 or R12 is hydrogen;
- and
- reacting a compound of formula (IV) wherein at least one of R11 or R12 is hydrogen, or a salt thereof, with a compound of formula (VI)
- Q—C(═O)—Z (VI)
- wherein
- Q is a defined above;
- and
- —C(═O)—Z is an acyl precursor.
45 more elements
Dependencies are inferred from the claim text.