Oxobenzofuranylide-dihydroindolone

• US 6,503,937 B1
• Filed: 04/03/2001
• Issued: 01/07/2003
• Est. Priority Date: 10/22/1998
• Status: Expired due to Fees

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Nesvadba, Peter, Jandke, Joachim
• Primary Examiner(s): Chang, Ceila
• Assistant Examiner(s): WRIGHT, SONYA N
• Application Number:
  US09/806,741
• Time in Patent Office: 644 Days
• Field of Search: 548/463, 514/414
• US Class Current: 514/414
• CPC Class Codes: C07D 405/04 directly linked by a ring-member-to-ring-member bond

Abstract

Oxobenzofuranylidene-dihydroindolones of formulae trans-(Ia) and cis-(Ib)

and of formulae trans-(IIa) and cis-(IIb)

wherein

A₁ and A₂ are each independently of the other unsubstituted or mono- to tetra-substituted ortho-C₆-C₁₈arylene, and R₁ is hydrogen or an organic radical, with the proviso that when R₁ is hydrogen and A₂ is 1,2-phenylene, A₁ is not 9,10-anthraquinon-1,2-ylene, 4-chloro-3,5-dimethyl-1,2-phenylene or 3,5-dimethyl-1,2-phenylene, processes for their preparation and the use thereof.

Claims

1. An oxobenzofuranylidene-dihydroindolone of formula trans-(Ia) or cis-(Ib)

wherein

A₁ and A₂ are each independently of the other unsubstituted or mono- to tetra-substituted 1,2-phenylene and

R₁ is hydrogen, C₁-C₂₅alkyl, C₅-C₁₂cycloalkyl, C₆-C₂₄aryl, a heteroaromatic radical, —

(CH₂)_n—

COR₂ or —

(CH₂)_m—

OR₃,

wherein R₂ is hydroxy, —

OX, or, unsubstituted or mono- or poly-substituted by hydroxy, —

OX or by amino, C₁-C₂₅alkoxy, C₁-C₂₅alkylamino or C₁-C₂₅dialkylamino, di(C₆-C₂₄aryl)amino, C₁-C₁₂alkyl, C₂-C₂₄alkenyl, and

X is a cation, and

R₃ is hydrogen or —

CO—

(C₁-C₂₅alkyl), and

n and m denote each independently of the other a whole number in the range from 0 to 6, and

a single C—

C bond also may have been replaced by a corresponding ether unit, C—

O—

C, with the proviso that, when R₁ is hydrogen and A₂ is 1,2-phenylene, A₁ is not 4-chloro-3,5-dimethyl-1,2-phenylene or 3,5-dimethyl-1,2-phenylene.

2. An oxobenzofuranylidene-dihydroindolone according to claim 1, wherein A₁ is

and A₂ is

  wherein

R₈, R₉, R₁₁, R₁₀, R₁₂, R₁₃, R₁₄ and R₁₅ are each independently of the others hydrogen, halogen, cyano, —

NO₂, —

R₁₆, —

NR₁₇R₁₈, —

NR₁₉COR₁₇, —

NR₁₉COOR₁₇, —

N═

CR₁₇R₁₈, —

CONR₁₉R₂₀, —

OR₁₇, —

O—

(C₁-C₁₂alkylene)—

COOX, —

O—

(C₁-C₁₂alkylene)—

COOH,

—

O—

(C₁-C₁₂alkylene)—

O—

CO—

R₁₇, —

O—

(C₁-C₁₂alkylene)—

COOR₁₇,

—

O—

(C₁-C₁₂alkylene)—

CONR₁₉R₂₀, —

O—

(C₁-C₁₂alkylene)—

OR₁₇,

—

(C₁-C₁₂alkylene)—

O—

CO—

R₁₇,

—

(C₁-C₁₂alkylene)—

OR₁₇, —

COOR₁₇, —

(C₁-C₁₂alkylene)—

COOR₁₇,

—

(C₁-C₁₂alkylene)—

CONR₁₉R₂₀, —

(C₁-C₁₂alkylene)—

COOX, —

(C₁-C₁₂alkylene)—

COOH,

—

COOX, —

COOH, —

SR₁₇, —

SOR₁₇, —

SO₂R₁₇, —

SO₂NR₁₉R₂₀, —

SO₃R₁₇, SO₃H or SO₃X,

 

wherein

R₁₇, R₁₈, R₁₉ and R₂₀ are each independently of the others hydrogen or R₁₆, and

R₁₆ is, unsubstituted or mono- or poly-substituted by halogen, hydroxy, amino, oxo, carboxy, cyano, —

COOR₁₈ or by —

COOX, C₁-C₂₅alkyl, C₅-C₁₂cycloalkyl or C₂-C₂₄alkenyl, which may be uninterrupted or interrupted one or more times by O, S or N—

(C₁-C₂₅alkyl), N—

(C₂-C₂₄alkenyl) when the alkyl has more than two and the alkenyl more than three carbon atoms, or is, unsubstituted or mono- or poly-substituted by halogen, nitro, cyano, —

OR₁₈, —

SR₁₈, —

NR₁₉R₂₀, —

CONR₁₉R₂₀, —

COOR₁₈, —

COOX, —

COOH, —

SO₂R₁₈, —

SO₂NR₁₉R₂₀, —

SO₃R₁₈, —

SO₃X, —

SO₃H, —

NR₁₉COR₁₈ or by —

NR₁₉COOR₁₈, C₆-C₁₈aryl, C₇-C₁₈aralkyl or heteroaryl or

R₁₉ and R₂₀, together with the nitrogen atom linking them, are unsubstituted or mono- to tetra-C₁-C₄alkyl-substituted pyrrolidinyl, piperidyl, piperazinyl or morpholinyl, or are carbazolyl, phenoxazinyl or phenothiazinyl.

3. A composition comprising at least one oxobenzofuranylidene-dihydroindolone according to claim 1.

4. A process for the preparation of an oxobenzofuranylidene-dihydroindolone of formula trans-(Ia) or cis-(Ib) according to claim 1 by reaction of a benzofuranone compound with an isatin compound in the presence of an acidic or basic catalyst, which process comprises reacting a compound of formula (XXIX)

wherein A₁ is unsubstituted or mono- to tetra-substituted 1,2-phenylene, with a compound of formula (XXX) or (XXXa)

 

wherein

Y is O, S, NH, N—

(C₁-C₂₄alkyl), N—

(C₅-C₁₈aryl) or N—

(C₇-C₂₈aralkyl) and

Hal is halogen, and

A₂ is unsubstituted or mono- to tetra-substituted 1,2-phenylene.

5. An oxobenzofuranylidene-dihydroindolone according to claim 1, wherein A₁ is

wherein

R₈, R₉, R₁₁, R₁₀, R₁₂, R₁₃, R₁₄ and R₁₅ are each independently of the others hydrogen, halogen, cyano, —

NO₂, —

R₁₆, —

NR₁₇R₁₈, —

NR₁₉COR₁₇, —

NR₁₉COOR₁₇, —

N═

CR₁₇R₁₈, —

CONR₁₉R₂₀, —

OR₁₇, —

O—

(C₁-C₁₂alkylene)—

COOX, —

O—

(C₁-C₁₂alkylene)—

COOH,

—

O—

(C₁-C₁₂alkylene)—

O—

CO—

R₁₇, —

O—

(C₁-C₁₂alkylene)—

COOR₁₇,

—

O—

(C₁-C₁₂alkylene)—

CONR₁₉R₂₀, —

O—

(C₁-C₁₂alkylene)—

OR₁₇,

—

(C₁-C₁₂alkylene)—

O—

CO—

R₁₇,

—

(C₁-C₁₂alkylene)—

OR₁₇, —

COOR₁₇, —

(C₁-C₁₂alkylene)—

COOR₁₇,

—

(C₁-C₁₂alkylene)—

CONR₁₉R₂₀, —

(C₁-C₁₂alkylene)—

COOX, —

(C₁-C₁₂alkylene)—

COOH,

—

COOX, —

COOH, —

SR₁₇, —

SOR₁₇, —

SO₂R<sub>17, —

SO2</sub>NR₁₉R₂₀, —

SO₃R₁₇, SO₃H or SO₃X,

 

wherein

R₁₇, R₁₈, R₁₉ and R₂₀ are each independently of the others hydrogen or R₁₆, and

R₁₆ is, unsubstituted or mono- or poly-substituted by halogen, hydroxy, amino, oxo, carboxy, cyano, —

COOR₁₈ or by —

COOX, C₁-C₂₅alkyl, C₅-C₁₂cycloalkyl or C₂-C₂₄alkenyl, which may be uninterrupted or interrupted one or more times by O, S or N—

(C₁-C₂₅alkyl), N—

(C₂-C₂₄alkenyl) when the alkyl has more than two and the alkenyl more than three carbon atoms, or is, unsubstituted or mono- or poly-substituted by halogen, nitro, cyano, —

OR₁₈, —

SR₁₈, —

NR₁₉R₂₀, —

CONR₁₉R₂₀, —

COOR₁₈, —

COOX, —

COOH, —

SO₂R₁₈, —

SO₂NR₁₉R₂₀, —

SO₃R₁₈, —

SO₃X, —

SO₃H, —

NR₁₉COR₁₈ or by —

NR₁₉COOR₁₈, C₆-C₁₈aryl, C₇-C₁₈aralkyl or heteroaryl, or

R₁₉ and R₂₀, together with the nitrogen atom linking them, are unsubstituted or mono- to tetra-C₁-C₄alkyl-substituted pyrrolidinyl, piperidyl, piperazinyl or morpholinyl, or are carbazolyl, phenoxazinyl or phenothiazinyl.