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US 2017/0291871 A1Published application
2,2' -diaminobiaryls having one primary and one secondary amine
AssigneeEvonik Degussa GmbH
InventorsKatrin Marie DYBALLA, Robert FRANKE, Dirk FRIDAG, Siegfried R. WALDVOGEL, Bernd ELSLER, Mathias ENDERS
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Abstract
Novel 2,2′-diaminobiaryls having one primary and one secondary amine and an electrochemical process for preparation thereof.
Claims14
Compound having one of the general structures (I) to (III):
- where
- R1, R2, R3, R4, R1′, R2′, R3′ are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —OC—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —CN, —N[(C1-C12)-alkyl]2;
- R4′ is selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —CN, —N[(C1-C12)-alkyl]2;
- R5, R6, R7, R8, R9, R10, R5′, R6′, R7′, R8′, R9′, R10′ are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —N[(C1-C12)-alkyl]2;
- where the alkyl and aryl groups mentioned may be substituted;
- and, in the formula (I), the two radicals in at least one of the four following radical pairs are not the same radical:
- R1 and R1′, R2 and R2′, R3 and R3′, R4 and R4′,
- and, in the formula (III), the two radicals in at least one of the six following radical pairs are not the same radical:
- R5 and R5′, R6 and R6′, R7 and R7′, R8 and R8′, R9 and R9′, R10 and R10′,
- X1 is selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
- X2, X2′ are selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
- X3 is selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphenyl.
15 more elements
Process for preparing 2,2′-diaminobiaryls, comprising the process steps of:
- a1) reacting a compound of the formula (IVa):
- with X11 to give (IVb)
- b1) reacting a compound of the formula (Va):
- with X11′ to give (Vb)
- c1) electrochemically coupling:
- (IVb) with (Vb) to give (VIa)
- with use of the compound having the higher oxidation potential in excess:
- d1) selectively detaching X11′, with conversion of (VIa) to (VIb):
- where
- R11, R12, R13, R14, R11′, R12′, R13′, R14′ are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —CN, —N[(C1-C12)-alkyl]2;
- where the alkyl and aryl groups mentioned may be substituted;
- X11 and X11′ are selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
- and X11 is not the same radical as X11′.
12 more elements
Process for preparing 2,2′-diaminobiaryls, comprising the process steps of:
- a2) reacting a compound of the formula (VIIa):
- with X12 to give (VIIb):
- b2) reacting a compound of the formula (VIIIa):
- with X12′ to give (VIIIb):
- c2) electrochemically coupling:
- (IIIb) with (VIIIb) to give (IXa)
- with use of the compound having the higher oxidation potential in excess:
- d2) selectively detaching X12′ or X12, with conversion of (IXa) to (Xa) or (Xb):
- where
- R11, R12, R13, R14 are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —N[(C1-C12)-alkyl]2;
- R15′, R16′, R17′, R18′, R19′, R20′ are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —N[(C1-C12)-alkyl]2;
- where the alkyl and aryl groups mentioned may be substituted;
- X12 and X12′ are selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
- and X12 is not the same radical as X12′.
14 more elements
Process for preparing 2,2′-diaminobiaryls, comprising the process steps of:
- a3) reacting a compound of the formula (XIa):
- with X13 to give (XIb):
- b3) reacting a compound of the formula (XIIa):
- with X13′ to give (XIIb):
- c3) electrochemically coupling:
- (XIb) with (XIIb) to give (XIIIa)
- with use of the compound having the higher oxidation potential in excess:
- d3) selectively detaching X13′, with conversion of (XIIIa) to (XIIIb):
- where
- R15, R16, R17, R18, R19, R20, R15′, R16′, R17′, R18′, R19′, R20′ are selected from:
- —H, —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C1-C12)-alkyl, —CONH—(C1-C12)-alkyl, —CO—(C1-C12)-alkyl, —CO—(C6-C20)-aryl, —COOH, —OH, —SO3H, —N[(C1-C12)-alkyl]2;
- where the alkyl and aryl groups mentioned may be substituted;
- X13 and X13′ are selected from:
- tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
- and X13 is not the same radical as X13′.
12 more elements
Dependencies are inferred from the claim text.