A Convenient Synthesis of Octasubstituted Phthalocyanines

Pawlowski, Georg; Hanack, Michael

doi:10.1055/s-1980-28993

Cited by 88 publications

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“…We envisioned that a 5-substituted iminothioamide should self-condense in one direction to form exclusively a 2,9,16,23-tetrasubstituted phthalocyanine as one isomer, because the irnino group on one side of the molecule should displace selectively the methythio group on the other side of a second molecule. It turns out that treatment of phthalonitrile (3) with hydrogen sulfide gas gives 1-imino-3-isoindoline (4) directly, as reported by Baguley and Elvidge (12), but 4 does not readily condense to phthalocyanine under normal conditions (4,5). Despite the fact that we were unable to successfully S-alkylate dithioamides (1 1) under a variety of conditions, we found that the iminothioamide 4 is readily alkylated to a separable mixture of N-methyl-2,3-dihydro-3-thioxo-1 H-isoindol-1-one (5) and 1-imino-3-methylthioisoindolenine (6).…”

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confidence: 68%

“…Most tetrasubstituted phthalocyanines are prepared by self-condensation of a suitable 3 or 4-substituted phthalonitrile or derivative (4,5). For example, the isoindoline of 4-neopentoxyphthalonitrile will, upon condensation, give not only 2,9,16,23-tetraneopentoxyphthalocyanine (1) but also the 2,10,16,24-, 2,9,17,24-, and 2,9,16,24-tetraneopentoxyphthalocyanine isomers (6,7).…”

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confidence: 99%

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Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pure isomer

Greenberg¹,

Lever²,

Leznoff³

1988

Can. J. Chem.

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, 1059 (1988). Treatment of 4-neopentoxyphthalonitrile with hydrogen sulfide gas yielded 1-irnino-6-neopentoxy-3-thioisoindoline and 1-irnino-5-neopentoxy-3-thioisoindoline, which on alkylation with iodomethane gave 1 -imino-3-methylthio-6-neopentoxyisoindolenine and 1-imino-3-methylthio-5-neopentoxyisoindolenine. The methylthioisoindolenines readily condensed at room temperature to a mixture of tetrasubstituted phthalocyanines and a series of linear open-chained purple compounds characteristic of isoindigos, while condensation at -20°C in the presence of zinc acetate gave, in at least one experiment, 2,9,16,23-tetraneopentoxyphthalocyanine as a pure isomer. The low temperature formation of phthalocyanines is remarkable and the syntheses described herein provide guidelines for the synthesis of pure isomers of 2,9,16,23-tetrasubstituted phthalocyanines. The purple and red compounds are shown to have isoindigo structures rather than a ring-opened phthalocyanine structure as previously reported.SHAFRIRA GREENBERG, A. B. P. LEVER et CLIFFORD C. LEZNOFF. Can. J. Chem. 66, 1059 (1988). La rkaction du nkopentoxy-4 phtalonitrile et du sulfure d'hydrogbne gazeux conduit i I'imino-1 ntopentoxy-6 thio-3 isoindoline et a I'imino-1 nkopentoxy-5 thio-3 isoindoline qui, par alkylation avec I'iodomkJhane, conduisent B I'imino-1 mkthylthio-3 nkopentoxy-6 isoindoline et a I'imino-1 mkthylthio-3 nkopentoxy-5 isoindoline. A la temptrature ambiante, les mCthylthioisoindolines se condensent facilement pour donner un mklange de phtalocyanines tttrasubstitukes et une strie de composts linkaires pourpres caractkristiques des isoindigos; par ailleurs, une condensation B -20°C, en prtsence d'acttate de zinc, a conduit-au moins dans une experience-i la tttrankopentoxy-2,9,16,23 phtalocyanine sous la forme d'un isomere pur. La formation de phtalocyanines 2 basse tempkrature est remarquable et les synthbses dtcrites dans ce travail fournissent des indications sur les mkthodes de synthese des isombres purs des phtalocyanines substitutes en 2,9,16,23. On a dtmontrt que les composts pourpre et rouge possedent des structures relikes B celle de I'isoindigo plut6t que des structures relikes a celle de la phtalocyanine qui avaient kt6 suggkrkes antkrieurement.[Traduit par la revue]Tetrasubstituted phthalocyanines having one substituent on each of the four benzo rings of phthalocyanine have been known for some time (1) but have received more attention recently due to their importance in electrocatalytic studies (2, 3). Most tetrasubstituted phthalocyanines are prepared by self-condensation of a suitable 3 or 4-substituted phthalonitrile or derivative (4, 5). For example, the isoindoline of 4-neopentoxyphthalonitrile will, upon condensation, give not only 2,9,16,23-tetraneopentoxyphthalocyanine (1) but also the 2,10,16,24-, 2,9,17,24-, and 2,9,16,24-tetraneopentoxyphthalocyanine isomers (6, 7). Indeed, we have shown that the 2,9,16,23-tetraneopentoxy hthalocyanine zinc(11) (2) derivative exhibited P peaks in its H nmr spectrum, indicating the presenc...

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confidence: 68%

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confidence: 99%

Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pure isomer

Greenberg¹,

Lever²,

Leznoff³

1988

Can. J. Chem.

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“…It turns out that treatment of phthalonitrile (3) with hydrogen sulfide gas gives l-imino-3-isoindoline (4) directly as reported by Baguley and Elvidge (12), but 4 does not readily condense to phthalocyanine under normal conditions (4,5).…”

Section: Amract (Continue On Reverse Of Necessary and Identity By Blomentioning

confidence: 56%

Approaches Towards the Synthesis of a 2,9,16,23-Tetrasubstitutedphthalocyanine as a Pure Isomer

Greenberg¹,

Lever²,

Leznoff³

1988

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“…Although symmetrical tetra (1-3) and octasubstituted (4)(5)(6) phthalocyanines are well known, the synthesis of simple mono-(7), disubstituted (8), and other unsymmetrical phthalocyanines (9, 10) remains a difficult problem. A typical symmetrical phthalocyanine synthesis involves the self-condensation of 5-substituted or 4,5-disubstituted-l,3-diiminoisoindolines (4,11).…”

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confidence: 99%

“…A typical symmetrical phthalocyanine synthesis involves the self-condensation of 5-substituted or 4,5-disubstituted-l,3-diiminoisoindolines (4,11). A simple strategy available to form unsymmetrical phthalocyanines is the mixed condensation of two different 1,3-diiminoisoindolines to obtain the desired mono-, di-, or trisubstituted phthalocyanines.…”

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confidence: 99%

The syntheses of mono- and disubstituted phthalocyanines using a dithioimide

Leznoff¹,

Greenberg²,

Khouw³

et al. 1987

Can. J. Chem.

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. J. Chem. 65, 1705Chem. 65, (1987.Hydrolysis of 5-neopentoxy-l,3-diiminoisoindoline gave 5-neopentoxy-l H-isoindole-l,3(2H)-dione (4-neopentoxyphthalimide), which, on treatment with Lawesson's reagent, yielded the thiophthalimides, 5-neopentoxy-lH-isoindole-l,3(2H)-dithione, 2,3-dihydro-6-neopentoxy-3-thioxo-1 H-isoindo-l o n e and 2,3-dihydro-5-neopentoxy-3-thioxo-1 H-isoindo-1 -one. Attempted S-alkylations of the thiophthalimides resulted in the formation of P-isoindigos and N-alkylation products. In a new phthalocyanine synthesis crossed condensations of 1,3-diiminoisoindoline with 5-neopentoxy-1 H-isoindole-l,3(2H)-dithione yielded mixtures of phthalocyanines from which 2-neopentoxyphthalocyanine and 2,16-dineopentoxyphthalocyanine could be purified in part from other phthalocyanines. CLIFFORD C. LEZNOFF, SHAFRIRA GREENBERG, BEN KHOUW et A. B. P. LEVER. Can. J. Chem. 65, 1705Chem. 65, (1987. L'hydrolyse de la nkopentoxy-5 diimino-1,3 indoline conduit a la nkopentoxy-5 1H-isoindole (2H)-dione-1,3 (nkopentoxy-4 phtalimide) qui, par traitement avec le rkactif de Lawesson, fournit les thiophtalimides, ntopentoxy-5 lH-isoindole (2H)-dithione-1,3, dihydro-2,3 ntopentoxy-6 thioxo-3 1 H-isoindolone-1 et dihydro-2,3 ntopentoxy-5 thioxo-3 1 H-isoindolone-1 .Des essais de S-alkyler les thiophtalimides ont conduit A la formation de P-isoindigos et de produits de N-alkylation. Dans une nouvelle synthbse de la phtalocyanine, des condensations de la diimino-1,3 isoindoline avec la nkopentoxy-5 lH-isoindole (2H-dithione-1,3 ont conduit a des mClanges de phtalocyanines a partir desquels on a pu purifier en partie la ntopentoxy-2 phtalocyanine et la dintopentoxy-2,16 phtalocyanine.[Traduit par la revue]Although symmetrical tetra (1-3) and octasubstituted (4-6) phthalocyanines are well known, the synthesis of simple mono-(7), disubstituted (8), and other unsymmetrical phthalocyanines (9, 10) remains a difficult problem. A typical symmetrical phthalocyanine synthesis involves the self-condensation of 5-substituted or 4,5-disubstituted-l,3-diiminoisoindolines (4, 11). A simple strategy available to form unsymmetrical phthalocyanines is the mixed condensation of two different 1,3-diiminoisoindolines to obtain the desired mono-, di-, or trisubstituted phthalocyanines. In fact, condensation of 1,3-diiminoisoindoline (1) and 5-neopentoxy-1,3-diiminoisoindoline (2) does give mixtures of unsubstituted, mono-, di-, tri-, and tetraneopentoxyphthalocyanines (3-8) as expected when analyzed by mass spectr~scopy.~ We envisioned that a completely new approach to phthalocyanine synthesis was required. If we could perform a crossed condensation of substrates in which one of the substrates is unable to self-condense and if we could lower the temperature of phthalocyanine formation so that crossed condensation is favoured over self-condensation of the other substrate, then specifically substituted phthalocyanines could be formed as shown in Scheme 1.Although phthalic anhydrides self-condense, probably via phthalimides to form phthalocyanine...

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A Convenient Synthesis of Octasubstituted Phthalocyanines

Cited by 88 publications

References 0 publications

Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pure isomer

Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pure isomer

Approaches Towards the Synthesis of a 2,9,16,23-Tetrasubstitutedphthalocyanine as a Pure Isomer

The syntheses of mono- and disubstituted phthalocyanines using a dithioimide

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