C-Nucleophilic substitution in tetrachlorophthalonitrile — An approach to some new hexadecasubstituted phthalocyanines

2013 ◽  
Vol 17 (08n09) ◽  
pp. 799-806 ◽  
Author(s):  
Vladimir Negrimovsky ◽  
Konstantin Volkov ◽  
Kyrill Suponitsky ◽  
Evgeny Lukyanets
Keyword(s):  
Nucleophilic Substitution ◽  
Benzene Ring ◽  
Chlorine Atom ◽  
Diethyl Malonate ◽  
Methine Proton ◽  
Chlorine Atoms ◽  
High Acidity ◽  
Zinc Phthalocyanines ◽  
Atoms First

Reaction of tetrachlorophthalonitrile with some C -nucleophiles was studied. Only one chlorine atom was substituted regioselectively in the position 4 of benzene ring with diethyl malonate and malononitrile; no reaction occurred in case of bulkier diethyl ethylmalonate and ethylmalononitrile. In case of dimedone the domino substitution of two chlorine atoms, first with C -nucleophile followed by enolate O -nucleophile led to the mixture of two dibenzofuran derivatives. Remaining chlorine aroms n malonate and dibenzofuran derivatives were substituted with thiols, but in malononitrile derivative high acidity of methine proton led to the formation of stable carbanion under basic conditions that prevents further substitution. Hexadecasubstituted zinc phthalocyanines were synthesized from some new phthalonitriles.

The Synthesis of New Selenium-containing Heterocycles by the Oxidation Reaction of 2,4-Diaryltetrahydro-4H-selenochromenes

2020 ◽  
Vol 24 (15) ◽  
pp. 1663-1668
Author(s):  
Dmitriy Yurievich Direnko ◽  
Boris Ivanovich Drevko ◽  
Yaroslav Borisovich Drevko
Keyword(s):  
Nucleophilic Substitution ◽  
Chlorine Atom ◽  
Oxidation Reaction ◽  
Heterocyclic Fragment ◽  
Oxidative Aromatization

We have explored the reactions of tetrahydro-4H-selenochromenes in the presence of phosphoric pentachloride, and synthesized new condensate aroylbenzoselenophenes. During the reactions, tetrahydro-4H-selenochromenes with phosphoric pentachloride underwent oxidative aromatization and nucleophilic substitution for a chlorine atom of one of the protons in the alicyclic fragment. Also, the narrowing of the heterocyclic fragment occurred as in synthesized selenium-containing compounds earlier transformed into the corresponding condensate aroylbenzoselenophenes.

Three new staphylonuclear chloromolybdates : K6Mo3Cl12, (NH4)7Mo3Cl13,H2O, and Cs6Mo4Cl16

1965 ◽  
Vol 18 (3) ◽  
pp. 271 ◽  
Author(s):  
IR Anderson ◽  
JC Sheldon
Keyword(s):  
Solid State ◽  
Hydrochloric Acid ◽  
Absorption Spectra ◽  
Oxidation State ◽  
Chlorine Atom ◽  
Reducing Agents ◽  
Ammonium Salts ◽  
Chlorine Atoms ◽  
Regular Triangle ◽  
New Compounds

The new compounds, K6Mo3IICl12; (NH4)7Mo3IICl13.H2O; and Cs6Mo4Cl16 (containing molybdenum in oxidation state +2.5) have been precipitated by the appropriate cation from solutions of molybdenum(II) acetate in 12M hydrochloric acid. The absorption spectra of potassium and ammonium salts are similar in the solid state and solution. Since the compounds are strong reducing agents and short-lived in solution, their formulation as a staphylonuclear (i.e. metal-clustered) trimer or tetramer rests on their diamagnetism, stoicheiometry, and spectral similarities. It is proposed that the chloromolybdates adopt entirely novel, compact polymers by stacking the chlorine atoms into "close packed" layers. The Mo3Cl13 group consists of two layers of chlorine atoms (seven and six) generating three octahedral locations for the molybdenum atoms at the corners of a regular triangle. The Mo3Cl12 group is similar but deficient in one chlorine atom. The Mo4Cl16 group is related to Mo3Cl13 and consists of three layers of chlorine atoms (seven, six, and three) providing four octahedral locations for the molybdenum atoms at the corners of a tetrahedron.

Reaction of adamantanone, diamantanone, and their derivatives with thionyl chloride

1987 ◽  
Vol 52 (8) ◽  
pp. 2028-2034 ◽  
Author(s):  
Josef Janků ◽  
Jiří Burkhard ◽  
Luděk Vodička
Keyword(s):  
Hydrogen Chloride ◽  
Carbonyl Group ◽  
Chlorine Atom ◽  
Thionyl Chloride ◽  
Reaction Rate ◽  
Axial Position ◽  
Chlorine Atoms

In reaction of adamantanone, diamantanone, and their chloro or oxo derivatives with thionyl chloride the oxo group is replaced with two chlorine atoms under formation of geminal dichloro derivatives. The presence of a chlorine atom or an oxo group in both ketones reduces the reaction rate. The reaction rate decreases with decreasing distance between the substituent and the carbonyl group. Ketones with chlorine atom in α- or β-axial position do not react with thionyl chloride. The reaction is accelerated by hydrogen chloride whereas in the presence of pyridine no reaction was observed.

Simple Synthesis of Fused Thiazolo[4,5-b]pyridines through Successive SNAr Processes

Synlett ◽  
2020 ◽  
Author(s):  
Alexey M. Starosotnikov ◽  
Maxim A. Bastrakov ◽  
Vadim V. Kachala ◽  
Ivan V. Fedyanin ◽  
Tatyana A. Klimova ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Nitro Group ◽  
Chlorine Atom ◽  
Simple Synthesis ◽  
Smiles Rearrangement ◽  
One Pot

AbstractA convenient process is described for the synthesis of novel thiazolo[4,5-b]pyridines fused with triazole or pyrimidine rings. The base-promoted reactions of 2-chloro-3-nitropyridines with 1,3-(S,N)-binucleophiles (triazole-5-thiols, 4-oxopyrimidine-2-thiones) resulted in nucleophilic substitution of the chlorine atom and subsequent S–N-type Smiles rearrangement followed by nucleophilic substitution of the nitro group. Reactions with pyrimidine-2-thiones were carried out as one-pot processes while, in the case of triazole-5-thiols, isolation of intermediate substitution products was found to be preferable.

Synthesis and characterization of O- and S-bridged perfluoroalkylated metal-free and zinc phthalocyanines

2013 ◽  
Vol 17 (06n07) ◽  
pp. 555-563 ◽  
Author(s):  
İlke Gürol ◽  
Gülay Gümüş ◽  
Emel Musluoğlu ◽  
Yadigar Arslan ◽  
Vefa Ahsen
Keyword(s):  
Nucleophilic Substitution ◽  
Elemental Analysis ◽  
Synthesis And Characterization ◽  
Polar Solvents ◽  
Metal Free ◽  
Zinc Phthalocyanines ◽  
Ft Ir

The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocyanines ( ZnPc and H 2 Pc ) are reported. The compounds 1–5 have been prepared by nucleophilic substitution of 4-nitrophthalonitrile with 1H,1H,2H,2H-perfluorooctanethiol, 1H,1H,2H,2H-perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol, 1H,1H-perfluorotetradecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol, respectively. The compounds 6–8 have been prepared by the reaction of 1H,1H,2H,2H-perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol with 4,5-dichlororphthalonitrile, respectively. The compound 9 with thia-bridge has been synthesized from 4,5-dichlororphthalonitrile. Zinc and metal free phthalocyanines were obtained from the corresponding phthalonitrile derivatives. All compounds were characterized by using mass, 1 H , 19 F NMR, UV-vis and FT-IR as well as elemental analysis. Tetra substituted Zn ( II ) phthalocyanines are slightly soluble only in THF (Compound 4a and 7a are insoluble) but metal free phthalocyanines are not soluble. Octa substituted Zn ( II ) and metal free phthalocyanine are soluble in polar solvents such as THF and DMSO.

ChemInform Abstract: Nucleophilic Substitution of the Chlorine Atom in Diarylchloromethylphosphine Oxides.

ChemInform ◽  
1987 ◽  
Vol 18 (5) ◽  
Author(s):  
A. N. YARKEVICH ◽  
S. E. TKACHENKO ◽  
E. N. TSVETKOV
Keyword(s):  
Nucleophilic Substitution ◽  
Chlorine Atom

Synthesis of water-soluble cobalt and zinc phthalocyanines with cationic substituents

2013 ◽  
Vol 17 (08n09) ◽  
pp. 750-755 ◽  
Author(s):  
Vladimir Negrimovsky ◽  
Konstantin Volkov
Keyword(s):  
Organic Solvents ◽  
Water Soluble ◽  
Monomeric Form ◽  
Chlorine Atoms ◽  
Zinc Phthalocyanines

Hexadecasubstituted CoPc and ZnPc containing different number of N-methylpyridiniumoxy groups and chlorine atoms were synthesized. It was shown that increasing number of cationic groups leads both to increased solubility of complexes in dipolar aprotic organic solvents and in water, and to increased contribution of monomeric form in aggregation equilibrium in water up full disaggregation.

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