A Convenient Synthesis of Trifluoromethyl Substituted Phthalocyanines

Pawlowski, Georg; Hanack, Michael

doi:10.1080/00397918108064299

Cited by 18 publications

(5 citation statements)

References 11 publications

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“…Absorbances were determined using a Perkin-Elmer Lambda 2 spectrometer. The syntheses of compounds 3a , 7a , b , 9 , 11 , 13 , and 4,5-dibromocatechol ( 1c ) are described in the literature. 2,3-Dicyanohydroquinone ( 5c ) is commercially available.…”

Section: Methodsmentioning

confidence: 99%

“…The synthetic routes to the precursors of the substituted phthalocyaninatotitanium(IV) oxides 4a − c , 8a − c (dinitriles 3b , c and isoindolines 7a − c ), are shown in Scheme . The trifluoromethyl- and 2,2,2-trifluoroethoxy-substituted phthalocyaninatotitanium(IV) oxides ( 4a − c) are obtained from the dinitriles 3a − c 20 and titanium(IV) butoxide in 1-octanol or 1-pentanol, respectively, under the conditions given in Scheme .…”

Section: Synthesismentioning

confidence: 99%

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Study of Substituent Effects on the Photoconductivity of Soluble 2,(3)- and 1,(4)-Substituted Phthalocyaninato- and Naphthalocyaninatotitanium(IV) Oxides

et al. 1998

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Soluble alkyl (II, 8a,b), fluoroalkyl (4a), and fluoroalkoxy (4b,c, 8c) 1,(4)- or 2,(3)-substituted phthalocyaninato- and linear 2,(3)- and angular 1,(2)-annulated naphthalocyaninatotitanium(IV) oxides 10, 12, and 14 were synthesized and characterized with regard to their spectroscopic, photophysical, and photochemical properties. While alkyl- and fluoroalkoxy-substituted compounds are highly soluble in nonpolar solvents, e.g., hexane, fluoroalkyl-substituted compounds are better soluble in polar aprotic solvents such as acetone. The stability against photooxidation in solution is enhanced on going from alkylated phthalocyanines 1,(4)-(C5H11)8PcTiO (8a), 1,(4)-(C6H13)8PcTiO (8b), and 2,(3)-(C4H9)8PcTiO (II) to fluorinated phthalocyanines 2,(3)-(CF3)4PcTiO (4a), 2,(3)-(CF3CH2O)4PcTiO (4b), and 2,(3)-(CF3CH2O)8PcTiO (4c), from phthalocyanines to naphthalocyanines (tert-butyl)4-2,(3)-NcTiO (10), 1,(2)-NcTiO (12), and (tert-butyl)4-1,(2)-NcTiO (14), and on going from 2,(3)-substituted 4a−c to 1,(4)-substituted phthalocyanines 8a−c. Thin films of these compounds, prepared by either vacuum deposition or spin casting, are classified into three types according to increasing intermolecular π−π interactions. Type α films, characterized by absence of exciton splitting, are formed from 1,(4)-substituted phthalocyanines 8a−c. These films show low dark conductivities and photoconductivities and are considerably sensitive to photooxidation. Type β films, characterized by weak exciton splitting, are formed from fluorinated phthalocyanines 4a−c as well as from rapidly deposited 2,(3)-substituted phthalocyanines II and the unsubstituted PcTiO (I). These films show enhanced photoconductivity and are generally more stable against photooxidation than type α films. Type γ films, formed by slow deposition of II, 10 and unsubstituted phthalocyanine I, are classified by a largely red-shifted B-band absorbing in the near-IR. These films are highly photosensitive as well as stabilized against photooxidation. Steady-state photoconductivities and dark conductivities in thin films are strongly dependent on oxygen partial pressure. Alkylated PcTiO's such as 8a, 8b, and II are found to be p-type conductors (positive oxygen influence on conductivities) like unsubstituted PcTiO (I), whereas angularly annulated naphthalocyanines such as 12 and 14 as well as fluorinated PcTiO's 4a−c are n-type conductors (negative oxygen influence on conductivity). These findings are rationalized by comparison with experimental and theoretical literature data.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Study of Substituent Effects on the Photoconductivity of Soluble 2,(3)- and 1,(4)-Substituted Phthalocyaninato- and Naphthalocyaninatotitanium(IV) Oxides

et al. 1998

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“…To synthesize the series of symmetrical bis(ammonio)alkane compounds 14 − 20 and the nonsymmetrical analogues 7 − 13 the commercially nonavailable starting anhydrides were synthesized by conversion of the 1,2-dicarboxylic acids by acetic anhydride according to procedures described in the literature. − The phthalimido-like propylamine derivatives 21 − 27 , 29 , and 31 − 32 , and 1,2- and 1,8-naphthalimidopropylamines 28 , 30 , and 33 were obtained by refluxing, in toluene and catalytic amount of p -toluenesulfonic acid, equimolar amounts of the phthalic-like anhydrides and the naphthalic anhydrides, respectively, with the corresponding N 1 , N 1 -dimethylpropane-1,3-diamines, using a water separator (Scheme ). To obtain the nonsymmetric W84-derivatives, the phthalimidopropylamines 22 , 25 , and 31 − 33 , respectively, were stirred with 1,6-dibromohexane for several days at room temperature and 50 °C, respectively, to give the alkylated compounds 34 − 38 (Scheme ).…”

Section: Chemistrymentioning

confidence: 99%

Systematic Development of High Affinity Bis(ammonio)alkane-type Allosteric Enhancers of Muscarinic Ligand Binding

et al. 2003

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Bis(ammonio)alkane compounds carrying lateral phthalimidopropyl substituents on the nitrogen atoms belong to the archetypal muscarinic allosteric agents. Herein, a series of symmetrical and nonsymmetrical compounds was synthesized in which the phthalimide residues were replaced by differently substituted imide moieties. The allosteric action was measured in porcine heart muscarinic M(2) receptors using [(3)H]N-methylscopolamine (NMS) as a ligand for the orthosteric receptor site in equilibrium binding and dissociation experiments. 1,8-Naphthalimido residues conferred an up to 100-fold gain in affinity leading into the low nanomolar range, while the inhibition of NMS binding was maintained. Additional propyl chain methylation was accompanied by an allosteric elevation of orthosteric ligand binding. In general, the gain in allosteric activity achieved by ring variation plus propyl chain methylation on one side of the molecule could not be augmented by symmetrical variations. The elevation of the ligand binding can be explained by different quantitative structure-activity relationships for the affinities to the free and the orthoster-liganded receptor.

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“…The synthetic route to host molecules 2 and 3 is outlined in Scheme 1. Crown ether 20 6 was treated with t-BuLi and allowed to react with 5-trifluoromethylphthalic anhydride (19) 7 to give 21 and its regioisomer 22 in respective yields of 35% and 50%. The phenolic allyl group of 21 was removed by Pd(PPh 3 ) 4 and sodium borohydride to give host 2 in 83% yield.…”

Section: Resultsmentioning

confidence: 99%

“…[1] 0 = 4.0 ¥ 10 -4 M.b [2] 0 = 4.0 ¥ 10 -5 M for 9 and 8.0 ¥ 10 -5 M for 10. c [5] 0 = 5.0 ¥ 10 -5 M. d[7] 0 = 2.0 ¥ 10 -4 M for 9 and 1.0 ¥ 10 -4 M for 10. e [8] 0 = 5.0 ¥ 10 -5 M. f Ka(9) and Ka(10) are association constants for 9 and 10, respectively. g SI = (Ka ¥ e)/(Ka 1 ¥ e 1 ).…”

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Development of highly sensitive and selective molecules for detection of spermidine and spermine

et al. 2009

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A Convenient Synthesis of Trifluoromethyl Substituted Phthalocyanines

Cited by 18 publications

References 11 publications

Study of Substituent Effects on the Photoconductivity of Soluble 2,(3)- and 1,(4)-Substituted Phthalocyaninato- and Naphthalocyaninatotitanium(IV) Oxides

Study of Substituent Effects on the Photoconductivity of Soluble 2,(3)- and 1,(4)-Substituted Phthalocyaninato- and Naphthalocyaninatotitanium(IV) Oxides

Systematic Development of High Affinity Bis(ammonio)alkane-type Allosteric Enhancers of Muscarinic Ligand Binding

Development of highly sensitive and selective molecules for detection of spermidine and spermine

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