KR20100057779A - Method of preparing naphthalocyanines - Google Patents

Abstract

A method of preparing a naphthalocyanine is provided. The method comprises the steps of: providing a tetrahydronaphthalic anhydride; converting said tetrahydronaphthalic anhydride to a benzisoindolenine; and macrocyclizing said benzisoindolenine to form a naphthalocyanine.

Description

Production method of naphthalocyanine {METHOD OF PREPARING NAPHTHALOCYANINES}

The present application generally relates to an improved method for preparing naphthalocyanine. It was primarily developed to reduce the cost of current naphthalocyanine synthesis methods and to facilitate the mass production of these compounds.

The use of naphthalocyanine as an IR-absorbing dye has already been disclosed. Naphthalocyanine, and especially gallium naphthalocyanine, have low absorption in the visible range and strong absorption in the near-infrared range (750-810 nm). Thus, naphthalocyanine is an attractive compound for invisible ink applications. Applicants' U.S. Pat.Nos. 7,148,345 and 7,122,076, the contents of which are incorporated herein by reference, provide for the preparation of inks suitable for printing coded data that is invisible (or hardly visible) on the substrate. The use of naphthalocyanine dyes in is described in detail. Detection of coded data by the optical sensing device can be used to induce a response in a remote computer system. Thus, the substrate is bidirectional with the encoded data printed thereon.

Applicants' netpage and Hyperlabel ^® systems, using an interactive description printed with coded data, are cross-referenced patents and patent applications (the contents of which are incorporated by reference). Incorporated in the specification).

In anticipation of widespread adoption of Netpage and Hyperlabel ^® technologies, there is a significant need to develop efficient synthesis of dyes suitable for use in inks for printing coded data. As previously implied above, naphthalocyanines and especially gallium naphthalocyanines are excellent candidates for these dyes, and as a result there is an increasing need to synthesize naphthalocyanines on a large scale, efficiently and in high yield.

Naphthalocyanines are attractive compounds for large scale synthesis. In US Pat. Nos. 7,148,345 and 7,122,076, efficient routes to naphthalocyanines via macrocyclization of naphthalene-2,3-dicarbonitrile have been described. Scheme 1 shows the route from naphthalene-2,3-dicarbonitrile (2) to sulfonated gallium naphthalocyanine (1), as described in US Pat. No. 7,148,345.

However, a problem with this route of naphthalocyanines is that the starting material (2) is expensive. Moreover, naphthalene-2,3-dicarbonitrile (2) is made from two expensive building blocks: tetrabromo- o -xylene (3) and fumaronitrile (4), none of which is several kilograms. It cannot be easily produced in quantities.

Thus, if naphthalocyanines can be used in large scale applications, there is a need to improve current synthetic methods.

Summary of the Invention

In a first aspect, a method for preparing naphthalocyanine is provided, comprising the following steps:

(Iii) providing tetrahydronaphthalic anhydride;

(Ii) converting said tetrahydronaphthalic anhydride to benzisoindolenin; And

(Iii) macrocycling the benziisoindolenin to form naphthalocyanine.

Optionally, tetrahydronaphthalic anhydride is represented by the following general formula (I):

From here:

R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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- 20} alkylcarbonylamino, C _5-20 aryl, C _5-20 arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryloxy, C ₅ Independently selected from _-20 heteroarylalkoxy or C _5-20 heteroarylalkyl.

Optionally, R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen.

Optionally, step (ii) comprises a one-pot conversion from tetrahydronaphthalic anhydride to benzisoindolenin salt. The one-pot conversion facilitates the synthesis of naphthalocyanines via the pathways described above and greatly improves yield and scalability.

Optionally, the benzisoindolenin salt is a nitrate salt, but other salts (eg, benzene sulfonate salts) are, of course, within the scope of the present invention.

Optionally, the one-pot conversion is performed by heating with a reagent mixture comprising ammonium nitrate.

Optionally, the reagent mixture comprises at least 2 equivalents of ammonium nitrate relative to tetrahydronaphthalic anhydride.

Optionally, the reagent mixture comprises urea.

Optionally, the reagent mixture comprises at least one additional ammonium salt.

Optionally, said additional ammonium salt is selected from ammonium sulfate and ammonium benzenesulfonate.

Optionally, the reagent mixture comprises a catalytic amount of ammonium molybdate.

Optionally, the heating is in the temperature range of 150-200 ° C.

The reaction can be carried out in the presence or absence of a solvent. Optionally, heating is carried out in the presence of an aromatic solvent. Examples of suitable solvents are nitrobenzene, biphenyl, diphenylether, mesitylene, anisole, phentol, dichlorobenzene, trichlorobenzene and mixtures thereof.

Optionally, benzisoindolenin is liberated from the benzisoindolenin salt using a base. Sodium methoxide is one example of a suitable base, but those skilled in the art will readily recognize other suitable bases.

Optionally, the benzisoindolenin is represented by the following general formula (II):

From here;

R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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- 20} alkylcarbonylamino, C _5-20 aryl, C _5-20 arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryloxy, C ₅ Independently selected from _-20 heteroarylalkoxy or C _5-20 heteroarylalkyl.

Optionally, the naphthalocyanine is represented by the following general formula (III):

From here;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each hydrogen , Hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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 _1-20 alkylcarbonylamino, C _5-20 aryl, C _{5 From -20} arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryl oxy, C _5-20 heteroarylalkoxy or C _5-20 heteroarylalkyl Independently selected;

M is absent or Si (A ¹ ) (A ² ), Ga (A ¹ ) (A ² ), Ga (A ¹ ), Mg, Al (A ¹ ), TiO, Ti (A ¹ ) (A ² ), ZrO, Zr (A ¹ ) (A ² ), VO, V (A ¹ ) (A ² ), Mn, Mn (A ¹ ), Fe, Fe (A ¹ ), Co, Ni, Cu, Zn, Sn, Sn (A ¹ ) (A ² ), Pb, Pb (A ¹ ) (A ² ), Pd and Pt;

A ¹ and A ² are axial ligands, which may be the same or different and are selected from —OH, halogen or —OR ^q ,

R ^q is 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 may be 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;

Optionally, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are All are hydrogen.

Optionally, M is Ga (A ¹ ) such as Ga (OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OMe); Wherein R ^q is CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OMe. To avoid uncertainties, ethers such as CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OMe are included within the definition of alkyl groups as detailed hereinbelow. Gallium compounds are preferred because they have excellent lightfastness and strong absorbance in the near infrared region and are virtually invisible to the human eye when printed on a page.

Optionally, step (iii) comprises heating of benzisoindolenin in the presence of a metal compound such as AlCl ₃ , or GaCl ₃ , or a corresponding metal alkoxide. This reaction can be carried out in the absence or presence of a suitable solvent such as toluene, nitrobenzene and the like. When metal alkoxides are used, the reaction can be catalyzed with a suitable base, such as sodium methoxide. Alcohols such as triethylene glycol monomethyl ether or glycols may also be present to aid naphthalocyanine formation. These alcohols may be axial ligands of naphthalocyanine or may be separated from the metal under reaction conditions. One skilled in the art will be able to easily optimize the conditions for naphthalocyanine formation from benzisoindolenin.

Optionally, the method further comprises sulfonating said naphthalocyanine. Sulfonate groups are useful for solubilizing naphthalocyanines in ink formulations, as described in our previous US Pat. Nos. 7,148,345 and 7,122,076.

In a second aspect, there is provided a method for performing a one-pot conversion of tetrahydronaphthalic anhydride to benzisoindolenin salt, the method heating the tetrahydronaphthalic anhydride with a reagent mixture comprising ammonium nitrate It involves doing.

This modification is advantageous in preventing the individual dehydrogenation step to form the naphthalene ring system. Ammonium nitrate performs the dual function of oxidation (dehydrogenation) and isoindolenin formation.

Isoindolenin salts produced according to the second aspect can be used for the synthesis of naphthalocyanines. Thus, this major reaction provides a significant improvement in the pathway to naphthalocyanine.

In general, any features of this second aspect reflect any of the features described above with respect to the first aspect.

In a third aspect, there is provided a method for preparing a sultine of the general formula (V) from a dihalogeno compound of the general formula (IV):

This method comprises the step of reacting a dihalogeno compound (IV) with a hydroxymethanesulfinate salt in a DMSO solvent to produce sultin (V);

From here;

R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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- 20} alkylcarbonylamino, C _5-20 aryl, C _5-20 arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryloxy, C ₅ Independently selected from _-20 heteroarylalkoxy or C _5-20 heteroarylalkyl; And

X is Cl, Br or I.

The method according to the third aspect surprisingly minimizes polymer by-products and improves yield when compared to the literature method for this reaction applying DMF as solvent. Their advantages are amplified when the reaction is carried out on a large scale (eg at least 0.3 mol, at least 0.4 mol or at least 0.5 mol scale).

Optionally, NaI is used to catalyze the coupling reaction when X is Cl or Br.

Optionally, metal carbonate bases (eg, Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO _3, etc.) are present.

Optionally, the hydroxymethanesulfinate salt is sodium hydroxymethanesulfinate (Rongalite ^™ ).

Optionally, R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen.

Optionally, the method further includes reacting the olefin with sultin (V) at high temperature (eg, about 80 ° C.) to produce a Diels-Alder adduct.

Optionally, the olefin is maleic anhydride and the Diels-Elder adduct is tetrahydronaphthalic anhydride.

Optionally, tetrahydronaphthalic anhydride is used as precursor for naphthalocyanine synthesis, as described herein.

Optionally, naphthalocyanine synthesis proceeds through the conversion of tetrahydronaphthalic anhydride to benzisoindolenin, as described herein.

Detailed description of the invention

As an alternative to dicarbonitrile, the general class of phthalocyanines is known to be prepared from isoindolenin. In US Pat. No. 7,148,345, benzisoindolenin (5) is proposed as a possible precursor to naphthalocyanine.

However, no efficient method for synthesizing benzisoindolenin (5) is known in the literature, and so far, dicarbonitriles such as naphthalene-2,3-dicarbonitrile (2) have been the only viable route to naphthalocyanine. .

Nevertheless, due to the potential very expensive cost of naphthalene-2,3-dicarbonitrile (2), we investigated a new route to benzisoindolenin (5), as shown in Scheme 2 below. did.

Tetrahydronaphthalic anhydride (6) was an attractive starting point because it is a known Diels-Elder adduct, which can be synthesized via the route shown in Scheme 3 below.

With reference to Scheme 2, the conversion of naphthalic anhydride (7) to benzisoindolenin (5) is similar to the known conversion of phthalic anhydride to isoindolenin (8), as described in WO98 / 31667. Expected to proceed.

However, many problems remain in the pathway shown in Scheme 2. First, the dehydrogenation of tetrahydronaphthalic anhydride 6 typically requires high temperature catalysis. Under these conditions, tetrahydronaphthalic anhydride 6 is easily sublimed, resulting in very poor yield. Second, the production of large scale tetrahydronaphthalic anhydride 6 is not known. Many small routes for these compounds are known in the literature, while they are generally difficult due to poor yield or scale problems.

The use of sultin as diene precursors is known and 1,4-dihydro-2,3-benzoxatin-3-oxide (10) is used for the synthesis of tetrahydronaphthalic anhydride (6) on a small scale ( Hoey, MD; Dittmer, DA J. Org. Chem. 1991, 56, 1947-1948). As shown in Scheme 4 below, this pathway begins with relatively inexpensive dichloro- o -xylene (11), but the possibility of increasing the scale of this reaction pathway is undesirable polymers in the sultin-forming step. Limited by the formation of byproducts. The formation of these by-products makes it difficult to reproduce the tetrahydronaphthalic anhydride 6 in high purity and high yield.

Nevertheless, the route shown in Scheme 4 may be attractive in terms of cost since both dichloro- o -xylene (11) and maleic anhydride are inexpensive materials.

While the sequence of reactions shown in Schemes 4 and 2 presents significant synthetic challenges, the inventors have surprisingly found that by using modified reaction conditions, benzisoindolenin (5) can be produced in high yield on a large scale. Revealed. Thus, the present invention enables the production of naphthalocyanine from inexpensive starting materials and represents a significant cost improvement over known synthetic methods starting from naphthalene-2,3-dicarbonitrile (2).

Referring to Scheme 5, a route to benzisoindolenin (5) is shown, which incorporates two synthetic improvements in accordance with the present invention.

Unexpectedly, the formation of sultin (10) is achieved by using DMSO as the reaction solvent in the conversion of dichloro- o -xylene (11) to 1,4-dihydro-2,3-benzoxatin-3-oxide (10). The reaction rate and selectivity were found to increase significantly. This is due to the known conditions of applying DMF as solvent, in which the formation of undesirable polymer byproducts is a major problem, especially for large scale production (Hoey, MD; Dittmer, DA J. Org. Chem . 1991, 56, 1947- 1948). Thus, the present invention provides a significant improvement in the synthesis of tetrahydronaphthalic anhydride (6).

The present invention also provides a significant improvement in the conversion of tetrahydronaphthalic anhydride (6) to benzisoindolenin (5). Surprisingly, it was found that the ammonium nitrate used for this step facilitates the oxidation of saturated ring systems as well as the conversion of tetrahydronaphthalic anhydride to benzisoindolenin. The conversion to tetrahydroisoindolenin was expected to proceed smoothly according to the isoindolenin-like systems described in WO98 / 31667. However, the dehydrogenation reaction under these reaction conditions advantageously provided a direct one-port route from tetrahydronaphthalic anhydride (6) to benzisoindolenin salt (12). This solves the problem of low yield dehydrogenation of tetrahydronaphthalic anhydride (6) in individual steps. Subsequent treatment of the salt 12 with a suitable base, such as sodium methoxide, liberates benzisoindolenin 5. As a result of these improvements, the entire reaction sequence from dichloro- o -xylene (11) to benzisoindolenin (5) is carried out very conveniently, and inexpensive starting materials and reagents are used (Scheme 5).

Benzisoindolenin (5) can be converted to any necessary naphthalocyanine using known conditions. For example, the preparation of gallium naphthalocyanine from benzisoindolenin (5) is illustrated herein. Continuous manipulation of the naphthalocyanine macrocycle can also be performed according to known protocols. For example, the sulfonation reaction can be carried out using an oleum, as described in US Pat. Nos. 7,148,345 and 7,122,076.

To date, the use of tetrahydronaphthalic anhydride (6) as a building block for naphthalocyanine synthesis has not been reported previously. However, it has now been found that tetrahydronaphthalic anhydride (6) is a viable intermediate in the synthesis of these important compounds. Moreover, it was found by the inventors that the route shown in Scheme 5 represents the most cost-effective synthesis of benzisoindolenins (5).

The term "aryl" is used herein to refer to an aromatic group, such as phenyl, naphthyl or trythysenyl. For example, C _6-12 aryl represents an aromatic group having 6-12 carbon atoms, excluding substituents. Of course, the term "arylene" denotes a divalent group corresponding to the monovalent aryl group described above. Where appropriate, any reference to aryl implicitly includes arylene.

The term “heteroaryl” denotes an aryl group in which one, two, three or four carbon atoms are substituted by a heteroatom selected from N, O or S. Examples of heteroaryl (or heteroaromatic) groups include pyridyl, benzimidazolyl, indazolyl, quinolinyl, isoquinolinyl, indolinyl, isoindolinyl, indolyl, isoindolyl, furanyl, thio Phenyl, pyrrolyl, thiazolyl, imidazolyl, oxazolyl, isoxazolyl, pyrazolyl, isoxazoloyl, piperazinyl, pyrimidinyl, piperidinyl, morpholinyl, pyrrolidinyl, isothiazolyl , Triazolyl, oxadizolyl, thiadizolyl, pyridyl, pyrimidinyl, benzopyrimidinyl, benzotriazole, quinoxalinyl, pyridazyl, coumarinyl and the like. Of course, the term “heteroarylene” denotes a divalent group corresponding to the monovalent heteroaryl group described above. Where appropriate, any reference to heteroaryl implicitly includes heteroarylene.

Unless stated otherwise, aryl and heteroaryl groups may be optionally substituted with 1, 2, 3, 4 or 5 substituents described below.

Where an optionally substituted group (eg with respect to an aryl group or heteroaryl group) is mentioned, the optional substituent (s) may be C _1-8 alkyl, C _1-8 alkoxy, — (OCH ₂ CH ₂ ) _d OR ^d (where d is an integer from 2 to 5000, and R ^d is H, C _1-8 alkyl or C (O) C _1-8 alkyl), cyano, halogen, amino, hydroxyl, thiol, -SR ^v , -NR ^u R ^v , nitro, phenyl, phenoxy, -CO ₂ R ^v , -C (O) R ^v , -OCOR ^v , -SO ₂ R ^v , -OSO ₂ R ^v , -SO ₂ OR ^v , -NHC (O) R ^v , -CONR ^u R ^v , -CONR ^u R ^v , -SO ₂ NR ^u R ^v , wherein R ^u and R ^v are hydrogen, C _1-12 alkyl, Independently from phenyl or phenyl-C _1-8 alkyl (eg benzyl). For example, where the group includes one or more substituents, other substituents may have other R ^u or R ^v groups.

The term "alkyl" is used herein to refer to alkyl groups in both straight and branched forms. Unless stated otherwise, an alkyl group may have 1, 2, 3 or 4 heteroatoms selected from O, NH or S. Unless stated otherwise, alkyl groups may also have one, two, or three double and / or triple bonds inserted. However, the term "alkyl" generally refers to alkyl groups with double or triple bond insertions. Where the "alkenyl" group is specifically mentioned, it is not intended to be interpreted in a limiting sense to the definition of "alkyl" above.

For example, when referring _to C _1-12 alkyl, this means that the alkyl group may comprise any number of carbon atoms between 1 and 12. Unless specifically stated, any reference to "alkyl" means C _1-20 alkyl, preferably C _1-12 alkyl or C _1-6 alkyl.

The term "alkyl" also includes cycloalkyl groups. As used herein, the term “cycloalkyl” includes cycloalkyl, polycycloalkyl, and cycloalkenyl groups as well as linear alkyl groups, such as cycloalkylalkyl groups, and combinations thereof. The cycloalkyl group may have one, two, or three heteroatoms selected from O, N or S inserted. However, the term "cycloalkyl" generally refers to a cycloalkyl group without heteroatom insertion. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclohexenyl, cyclohexylmethyl and adamantyl groups.

The term "arylalkyl" refers to groups such as benzyl, phenylethyl and naphthylmethyl.

The term "halogen" or "halo" is used herein to refer to any one of fluorine, chlorine, bromine and iodine. In general, however, halogen refers to chlorine or fluorine substituents.

Where "naphthalocyanine", "benzisoindolenin", "tetrahydronaphthalic anhydride" and the like are mentioned, this is understood to refer to the general class of compounds specified by their generic names, and any one It is not intended to refer to specific compounds. Reference to certain compounds is accompanied by a reference number.

The chiral compounds described herein were not given a stereo-descriptor. However, when the compounds may be in stereoisomeric form, all possible stereoisomers and mixtures thereof may be included (eg, all combinations including enantiomers, diastereomers and racemic mixtures, etc.).

Likewise, when compounds may exist in the form of several regioisomers or tautomers, all possible regioisomers, tautomers and mixtures thereof are included.

For the purpose of avoiding confusion, in the context of "including a (definite article) ~", the term "a" (or "an") means "at least one" and "one and only one". It does not mean. Where the term "at least one" is used specially, it should not be construed as limiting on the definition of "a".

Throughout the specification, modifications such as the terms "comprising", or "comprise" or "comprises" should be interpreted to include the components, integers, or steps mentioned, It does not exclude other ingredients, integers or steps.

The invention will be described with reference to the following figures and embodiments. However, it will of course be appreciated that the invention can be embodied in many other forms without departing from the scope of the invention, as defined in the appended claims.

The invention will be described in detail with reference to the following figures, in which:
1 is a ¹ H NMR spectrum of crude sultin (10) in d ₆ -DMSO;
2 is a ¹ H NMR spectrum of anhydride (8) in d ₆ -DMSO;
3 is a ¹ H NMR spectrum of crude benzisoindolenin salt in d ₆ -DMSO;
4 is an enlargement of the aromatic region of the ¹ H NMR spectrum shown in FIG. 3;
5 is a ¹ H NMR spectrum of benzisoindolenin in d ₆ -DMSO;
FIG. 6 is an enlargement of the aromatic region of the ¹ H NMR spectrum shown in FIG. 5; And
7 is a UV-VIS spectrum of naphthalocyanatogallium methoxytriethylene oxide in NMP.

Example 1

1.4-dihydro-2,3-benzoxatin-3-oxide (10)

Sodium hydroxymethanesulfinate (Rongalite ^™ ) (180 g; 1.17 moles) is suspended in DMSO (400 mL), dichloro-o-xylene (102.5 g; 0.59 moles), potassium carbonate (121.4 g; 0.988 moles) and sodium iodide (1.1 g; 7 mmol) was allowed to stir for 10 minutes before adding continuously. Prior to stirring the whole reaction mixture at room temperature, additional DMSO (112 mL) was used to flush out the residual material into the reaction mixture. The first endothermic reaction was mildly exothermic after about 1 hour, and the internal temperature rose to about 32-33 ° C. TLC (ethyl acetate / hexane 50:50) was carried out after the reaction, and it was confirmed that it was completed after 3 hours. The reaction mixture was diluted with methanol / ethyl acetate (20:80; 400 mL), the solids were removed by filtration and washed with additional methanol / ethyl acetate (20:80; 100 mL, 2 × 50 mL). The filtrate was transferred to a separating funnel and brine (1 L) was added. This produced more sodium chloride which had to be removed as a precipitate from the product mixture. The addition of water (200 mL) redissolved the sodium chloride. After the mixture was shaken to separate the organic layer, the aqueous layer was further extracted with methanol / ethyl acetate (20:80; 200 mL, 150 mL, 250 mL). The combined extracts were dried (Na ₂ SO ₄ ) and rotary evaporated (bath 37-38 ° C.). Additional solvent was removed under high vacuum to give sultin (10) (126 g) as a pale orange liquid, which was confirmed by ¹ H NMR spectroscopy to contain residual DMSO and ethyl acetate, relatively free of byproducts (FIG. 1). ).

Example 2

Tetrahydronaphthalic anhydride (6)

The crude sultin (126 g) from above was diluted in trifluorotoluene (100 mL) and then preheated (bath 80 ° C.) suspension of maleic anhydride (86 g; 0.88 mol) in trifluorotoluene (450 mL). Added. The residual sultin was washed into the reaction mixture with additional trifluorotoluene to give a final volume of 970 mL. The reaction mixture was heated at 80 ° C. for 15 hours and heating continued for an additional 8 hours after the addition of additional maleic anhydride (28.7 g; 0.29 mol) until TLC indicated that sultin was consumed. While maintaining 80 ° C., the solvent was removed by evaporation with a water aspirator, after which the residual solvent was removed under high vacuum. The wet solid was triturated with methanol (200 mL), filtered and washed with additional methanol (3 x 100 mL). After drying under high vacuum at 60 to 70 ° C. for 4 hours, tetrahydronaphthalic anhydride (6) (75.4 g; 64% from sultin (10)) was obtained as a fine white crystalline solid.

Example 3

As described in Example 2, sultin was prepared from dichloro-o-xylene (31.9 g; 0.182 moles), followed by maleic anhydride (26.8 g; 0.273) in toluene (300 mL total volume), as described above. Mole). This resulted in tetrahydronaphthalic anhydride (6) (23.5 g; 64%) as a white crystalline solid.

Example 4

1-amino-3-iminobenz [f] isoindolenin nitrate salt (12)

Urea (467 g; 7.78 mol) was added to a mixture of ammonium sulfate (38.6 g; 0.29 mol), ammonium molybdate (1.8 g) and nitrobenzene (75 mL) with a mechanical stirrer. The entire reaction mixture was heated using a heating mantle to about 130 ° C. (internal temperature) for 1 hour to cause melting of the urea. At this time the anhydride 6 (98.4 g; 0.99 mol) was added immediately as a solid. After 15 minutes, ammonium nitrate (126.4 g; 1.58 moles) was added under stirring (internal temperature 140 ° C.), with significant gas evolution. The reaction temperature was increased to 170-175 ° C. over 45 minutes and held for 2 hours 20 minutes. The viscous brown mixture was cooled to about 100 ° C. and then slowly added while stirring (400 mL) of methanol. The resulting suspension was poured onto a sintered glass funnel and the reaction flask was washed off with additional methanol (100 mL). After removing most of the methanol by gravity filtration, the brown solid was suction dried and washed with additional methanol (3 × 200 mL, 50 mL), air-dried overnight and dried under high vacuum for 1.5 h in a warm water bath. Benzisoindolenin salt (12) was obtained as fine brown powder (154.6 g), and it was confirmed by NMR analysis that it contained urea (5.43 ppm) and other salts (6.80 ppm). This material was used directly in the next step without further purification.

Example 5

1-amino-3-iminobenz [f] isoindolenin (7)

Crude nitrate 12 (154.6 g) was suspended in acetone (400 mL) with cooling to 0 ° C. in an ice / water bath. Sodium methoxide (25% in methanol; 284 mL; 1.3 moles) was slowly added dropwise through a dropping funnel at a rate sufficient to maintain an internal temperature of 0-5 ° C. When the addition was complete, the reaction mixture was poured into cold water (2 × 2 L) in two 2 L conical flasks. The mixture was then filtered over a sintered glass funnel and the solids were washed thoroughly with water (250 mL: 200 mL for each funnel). The fine brown solids were air dried for 2 days and then further dried under high vacuum to obtain benzisoindolenin (5) as fine brown powder (69.1 g; 73%).

Example 6

Naphthalocyanatogallium Methoxytriethylene Oxide

Gallium chloride (15.7 g; 0.089 mol) was dissolved in anhydrous toluene (230 mL) in a three-necked flask (1 L) equipped with a mechanical stirrer, heating mantle, thermometer and distillation outlet. After cooling the resulting solution to 10 ° C. in an ice / water bath, sodium methoxide in methanol (25%: 63 mL) was slowly added with stirring while maintaining the internal temperature below 25 ° C. to obtain a white precipitate. The mixture was then treated with triethylene glycol monomethyl ether (TEGMME; 190 mL) and then the whole reaction mixture was heated to evaporate both methanol and toluene (3 hours). The mixture was then cooled to 90-100 ° C. (internal temperature) by removing the heating mantle and then all of the benzisoindolenin (5) (69.0 g; 0.35 moles) from the previous step were immediately added as a solid and diethyl ether (30 mL) was used to wash the final traces into the reaction vessel. The reaction mixture was then placed in a preheated heating mantle to settle to an internal temperature of 170 ° C. after 20 minutes. Stirring was continued for 3 hours at 175-180 ° C., during which time dark rust / brown color appeared and release of ammonia occurred. The reaction mixture was cooled to about 100 ° C. prior to dilution with DMF (100 mL) and filtered through a sintered glass funnel overnight under gravity. Inhale dry the wet filter cake and, under suction, use DMF (80 mL), acetone (2 x 100 mL), water (2 x 100 mL), DMF (50 mL), acetone (2 x 50 mL: 100 mL) and diethyl ether (100 mL). Washed successively. After air drying briefly, the product was dried under high vacuum at 60-70 ° C. until constant weight. Naphthalocyanatogallium methoxytriethylene oxide was obtained as a microcrystalline dark blue / green solid (60.7 g; 76%); lambda _max (NMP) 771 nm (Figure 7).

Claims (20)

Method for preparing naphthalocyanine comprising the following steps:
(Iii) providing tetrahydronaphthalic anhydride;
(Ii) converting said tetrahydronaphthalic anhydride to benzisoindolenin; And
(Iii) macrocycling the benziisoindolenin to form naphthalocyanine. The method for preparing naphthalocyanine according to claim 1, wherein the tetrahydronaphthalic anhydride is represented by the following general formula (I):

From here:
R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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- 20} alkylcarbonylamino, C _5-20 aryl, C _5-20 arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryloxy, C ₅ Independently selected from _-20 heteroarylalkoxy or C _5-20 heteroarylalkyl. The method for producing naphthalocyanine according to claim 2, wherein R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen. The method of claim 1, wherein step (ii) comprises a one-pot conversion from tetrahydronaphthalic anhydride to benzisoindolenin salt. The method of claim 4, wherein the salt is a nitrate salt. The method of claim 4, wherein the one-pot conversion is performed by heating with a reagent mixture comprising ammonium nitrate. 7. The method of claim 6, wherein the reagent mixture comprises at least two equivalents of ammonium nitrate relative to tetrahydronaphthalic anhydride. The method of claim 6, wherein the reagent mixture comprises urea. 7. The method of claim 6, wherein the reagent mixture comprises at least one other ammonium salt. 10. The method of claim 9, wherein said at least one other ammonium salt is selected from ammonium sulfate and ammonium benzenesulfonate. 7. The method of claim 6, wherein the reagent mixture comprises a catalytic amount of ammonium molybdate. 7. The method of claim 6, wherein the heating is carried out in a temperature range of 150 ~ 200 ℃ naphthalocyanine. 13. The process of claim 12, wherein the heating is performed in the presence of a solvent selected from the group comprising nitrobenzene, biphenyl, diphenylether, mesitylene, anisole, phentol, dichlorobenzene, trichlorobenzene and mixtures thereof. Method for producing naphthalocyanine, characterized in that. 5. The method for producing naphthalocyanine according to claim 4, wherein the benzisoindolenin is liberated from the benzisoindolenin salt using a base. The method for producing naphthalocyanine according to claim 1, wherein the benzisoindolenin is represented by the following general formula (II):

From here;
R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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- 20} alkylcarbonylamino, C _5-20 aryl, C _5-20 arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryloxy, C ₅ Independently selected from _-20 heteroarylalkoxy or C _5-20 heteroarylalkyl. The method for producing naphthalocyanine according to claim 1, wherein the naphthalocyanine is represented by the following general formula (III):

From here;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each hydrogen , Hydroxyl, C _1-20 alkyl, C _1-20 alkoxy, amino, C _1-20 alkylamino, di (C _1-20 alkyl) 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 _1-20 alkylcarbonylamino, C _5-20 aryl, C _{5 From -20} arylalkyl, C _5-20 aryloxy, C _5-20 arylalkoxy, C _5-20 heteroaryl, C _5-20 heteroaryl oxy, C _5-20 heteroarylalkoxy or C _5-20 heteroarylalkyl Independently selected;
M is absent or Si (A ¹ ) (A ² ), Ga (A ¹ ) (A ² ), Ga (A ¹ ), Mg, Al (A ¹ ), TiO, Ti (A ¹ ) (A ² ), ZrO, Zr (A ¹ ) (A ² ), VO, V (A ¹ ) (A ² ), Mn, Mn (A ¹ ), Fe, Fe (A ¹ ), Co, Ni, Cu, Zn, Sn, Sn (A ¹ ) (A ² ), Pb, Pb (A ¹ ) (A ² ), Pd and Pt;
A ¹ and A ² are axial ligands, which may be the same or different and are selected from —OH, halogen or —OR ^q ,
R ^q is 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 may be 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. The method of claim 16, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ And R ₁₆ is all hydrogen to produce naphthalocyanine. The method for producing naphthalocyanine according to claim 16, wherein M is Ga (A ¹ ). The method of claim 1, wherein step (iii) comprises heating the benzisoindolenin in the presence of a metal compound. The method of claim 1, wherein the method further comprises the following steps:
(iv) sulfonating the naphthalocyanine.

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