ONE-POT SYNTHESIS OF BENZISOINDOLENINES USED IN THE PREPARATION OF NAPHTHALOCYANINES

• US 20100168413A1
• Filed: 02/21/2010
• Published: 07/01/2010
• Est. Priority Date: 08/01/2007
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: Silverbrook Research Pty Limited
• Inventors: Silverbrook, Kia, Indusegaram, Sutharsiny, Vonwiller, Simone Charlotte, Ridley, Damon Donald
• Granted Patent: US 7,947,844 B2
• Time in Patent Office: Days
• US Class Current: 540/122
• CPC Class Codes: C09B 47/06 Preparation from carboxylic acids or derivatives thereof , e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks

Abstract

A method of effecting a one-pot conversion of a tetrahydronaphthalic anhydride of formula (I):

to a nitrate salt of a benzisoindolenine of formula (II):

The method comprises heating the tetrahydronaphthalic anhydride of formula (I) with a reagent mixture comprising ammonium nitrate so as to effecting concomitant dehydrogenation during the conversion.

Claims

1. A method of effecting a one-pot conversion of a tetrahydronaphthalic anhydride of formula (I):

to a nitrate salt of a benzisoindolenine of formula (II);

said method comprising heating said tetrahydronaphthalic anhydride of formula (I) with a reagent mixture comprising ammonium nitrate so as to effecting concomitant dehydrogenation during the conversion, wherein;

R₁, R₂, R₃ and R₄ are each independently selected from the group consisting of;

hydrogen, hydroxyl, C_1-20 alkyl, C_1-20 alkoxy, amino, C_1-20alkylamino, di(C_1-20alkyl)amino, halogen, cyano, thiol, C_1-20 alkylthio, nitro, C_1-20 alkylcarboxy, C_1-20 alkylcarbonyl, C_1-20 alkoxycarbonyl, C_1-20 alkylcarbonyloxy, C_1-20alkylcarbonylamino, C_5-20 aryl, C_5-20 arylalkyl, C_5-20 aryloxy, C_5-20 arylalkoxy, C_5-20heteroaryl, C_5-20heteroaryloxy, C_5-20heteroarylalkoxy and C_5-20 heteroarylalkyl.

2. The method of claim 1, wherein R₁, R₂, R₃ and are all hydrogen.

3. The method of claim 1, wherein said reagent mixture comprises at least 2 equivalents of ammonium nitrate with respect to said tetrahydronaphthalic anhydride of formula (I).

4. The method of claim 1, wherein said reagent mixture comprises urea.

5. The method of claim 1, wherein said reagent mixture comprises at least one further ammonium salt.

6. The method of claim 5, wherein said at least one further ammonium salt is selected from the group consisting of:

ammonium sulfate and ammonium benzenesulfonate

7. The method of claim 1, wherein said reagent mixture comprises ammonium molybdate.

8. The method of claim 1, wherein said heating is within a temperature range of 150 to 200°

C.

9. The method of claim 8, wherein said heating is in the presence of a solvent selected from the group consisting of:

nitrobenzene, diphenyl, diphenyl ether, mesitylene, anisole, phenetole, dichlorobenzene, trichlorobenzene and mixtures thereof.

10. The method of claim 1, further comprising the step of:

liberating the benzisoindolenine of formula (II) from the benzisoindolenine nitrate salt using sodium methoxide.

11. The method of claim 10, further comprising the step of:

macrocyclizing said benzisoindolenine to form a naphthalocyanine of formula (III);

wherein;

M is absent or selected from Si(A¹)(A²), Ge(A¹)(A²), Ga(A¹), Mg, Al(A¹), TiO, Ti(A¹)(A²), ZrO, Zr(A¹)(A²), VO, V(A¹)(A²), Mn, Mn(A¹), Fe, Fe(A¹), Co, Ni, Cu, Zn, Sn, Sn(A¹)(A²), Pb, Pb(A¹)(A²), Pd and Pt;

A¹ and A² are axial ligands, which may be the same or different, and are selected from —

OH, halogen or —

OR^q;

R^q is selected from C_1-16 alkyl, C_5-20 aryl, C_5-20 arylalkyl, C_1-20 alkylcarbonyl, C_1-20 alkoxycarbonyl or Si(R^x)(R^y)(R^z); and

R^x, R^y and R^z may be the same or different and are selected from C_1-20 alkyl, C_5-20 aryl, C_5-20 arylalkyl, C_1-20 alkoxy, C_5-20 aryloxy or C_5-20 arylalkoxy.

12. The method of claim 11, wherein M is Ga(A¹).

13. The method of claim 11, wherein macrocyclizing step comprises heating said benzisoindolenine of formula (II) in the presence of GaCl₃.