Reactions of 4-phenyl-3H-1,2,4-triazole-3,5 (4H)-dione with alcohols and amines

1979 ◽  
Vol 57 (20) ◽  
pp. 2727-2733 ◽  
Author(s):  
Lê H. Dao ◽  
Donald Mackay
Keyword(s):  
Benzyl Alcohol ◽  
Title Compound ◽  
Secondary Amines ◽  
Secondary Alcohols ◽  
Bicyclic Compound ◽  
Tertiary Amines ◽  
Primary Alcohols ◽  
Complex Products ◽  
Diethyl Azodicarboxylate ◽  
Reaction Compound

Two equivalents of the title compound (1) react with one equivalent of primary alcohols to give good yields of nitrogen and 1-alkoxycarbonyl-2-N-phenylcarbamoyl-4-phenyl-1,2,4-triazolidine-3,5-di ones (3). With secondary alcohols or benzyl alcohol the major products are the ketone or benzaldehyde, while 3 are minor products. The latter can, however, be made the major products if pyridine is used to catalyze the reaction. Compound 3a dissociates on heating or in pyridine solution into the 1-methoxycarbonyltriazolidinedione 4.If alcohols are absent 1 is converted by pyridine or other tertiary amines into nitrogen and the bicyclic compound 9; if diethyl azodicarboxylate is present in the reaction compound 13 can be trapped.Primary and secondary amines react very rapidly with 1 to give nitrogen and complex products. It is likely that these are 1,2-dicarbamoyl-4-phenyltriazolidine diones, analogous to 3, and that they are very prone to dissociate in solution.

Best Synthetic Methods: Oxidation

2013 ◽  
Author(s):  
Douglass F. Taber
Keyword(s):  
Synthetic Methods ◽  
Secondary Amines ◽  
State University ◽  
Air Oxidation ◽  
Primary Alcohols ◽  
Ru Catalyst ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones ◽  
Diethyl Azodicarboxylate ◽  
The University

Karl A. Scheidt of Northwestern University described (Organic Lett. 2009, 11, 1651) the oxidation of primary alcohols such as 1 in the presence of an indole 2. The product 3, an active acylating agent, is readily converted to other esters and amides. K. Rajender Reddy of the Indian Institute of Chemical Technology, Hyderabad, developed (Tetrahedron Lett. 2009, 50, 2050) a protocol for the direct oxidation of a primary amine 4 to the corresponding nitrile 5. In the presence of ammonia, the same procedure converted aldehydes and primary alcohols into the nitriles. Several catalytic methods for the oxidation of alcohols to aldehydes and ketones have recently been put forward. René Grée of the Université de Rennes 1 found ( Tetrahedron Lett. 2009, 50, 1493) that ZnBr2 catalyzed the oxidation of alcohols with diethyl azodicarboxylate. Tsutomu Katsuki of Kyushu University designed (Tetrahedron Lett. 2009, 50, 3432) a Ru catalyst for the air oxidation of primary alcohols to aldehydes. Kazuaki Ishihara of Nagoya University showed (J. Am. Chem. Soc. 2009, 131, 251) that 1 mol % of 10 was sufficient to catalyze the oxidation of 6 to 7. With excess oxidant, 7 was carried on cleanly to 11. Nitroxyl radicals such as TEMPO have long been used to catalyze oxidations. Yoshiharu Iwabuchi of Tohoku University developed (J. Org. Chem. 2009, 74, 4619) a simple preparation of 13 , the most efficient such catalyst reported so far. This catalyst should also be useful for the oxidation reported by Professor Iwabuchi (Chem. Commun. 2009, 1739) of primary alcohols and aldehydes to the corresponding carboxylic acids. David S. Forbes of the University of South Alabama prepared (Tetrahedron Lett. 2009, 50, 1855) 16 by combining thioanisole with N-bromosuccinimide. The reagent 16 efficiently sulfenylated active methylene compounds. Jiri Srogl of the Academy of Sciences of the Czech Republic established (Organic Lett. 2009, 11, 843) conditions for the oxidation of primary and secondary amines to aldehydes and ketones. Olga A. Ivanova of Moscow State University demonstrated (Tetrahedron Lett. 2009, 50, 2793) that DMDO 21 could oxidize a sensitive amino cyclopropane such as 20 to the corresponding nitro compound.

Reaction of arylmethylenemalonaldehydes with some nucleophiles

1987 ◽  
Vol 52 (11) ◽  
pp. 2699-2709 ◽  
Author(s):  
Dalimil Dvořák ◽  
Zdeněk Arnold
Keyword(s):  
Inorganic Anions ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Primary And Secondary Amines ◽  
Dipolar Structure

Reaction of arylmethylenemalonaldehydes with tributylphosphine and tertiary amines affords compounds of dipolar structure whereas reaction with primary and secondary amines leads to 1,4-addition products. Salts of nucleophilic inorganic anions add to arylmethylenemalonaldehydes under formation of salts of substituted malonaldehydes.

Revisiting Sodium Hypochlorite Pentahydrate (NaOCl·5H2O) for the Oxidation of Alcohols in Acetonitrile without Nitroxyl Radicals

Synlett ◽  
2018 ◽  
Vol 29 (18) ◽  
pp. 2404-2407 ◽  
Author(s):  
Tsunehisa Hirashita ◽  
Yuto Sugihara ◽  
Shota Ishikawa ◽  
Yohei Naito ◽  
Yuta Matsukawa ◽  
...  
Keyword(s):  
Sodium Hypochlorite ◽  
Nitroxyl Radicals ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Oxidation Of Alcohols

Sodium hypochlorite pentahydrate (NaOCl·5H2O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. ­Aliphatic primary alcohols are not oxidized.

Ruthenium Pincer-Catalyzed Cross-Dehydrogenative Coupling of Primary Alcohols with Secondary Alcohols under Neutral Conditions

2012 ◽  
Vol 354 (13) ◽  
pp. 2403-2406 ◽  
Author(s):  
Dipankar Srimani ◽  
Ekambaram Balaraman ◽  
Boopathy Gnanaprakasam ◽  
Yehoshoa Ben-David ◽  
David Milstein
Keyword(s):  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Dehydrogenative Coupling ◽  
Neutral Conditions

scholarly journals Construction of a (NNN)Ru-Incorporated Porous Organic Polymer with High Catalytic Activity for β-Alkylation of Secondary Alcohols with Primary Alcohols

Polymers ◽  
2022 ◽  
Vol 14 (2) ◽  
pp. 231
Author(s):  
Yao Cui ◽  
Jixian Wang ◽  
Lei Yu ◽  
Ying Xu ◽  
David J. Young ◽  
...  
Keyword(s):  
Functional Group ◽  
Catalytic Efficiency ◽  
Organic Polymer ◽  
Pincer Ligands ◽  
High Catalytic Activity ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Solid Supports ◽  
Porous Organic Polymer ◽  
Heterogeneous And Homogeneous Catalysis

Solid supports functionalized with molecular metal catalysts combine many of the advantages of heterogeneous and homogeneous catalysis. A (NNN)Ru-incorporated porous organic polymer (POP-bp/bbpRuCl3) exhibited high catalytic efficiency and broad functional group tolerance in the C–C cross-coupling of secondary and primary alcohols to give β-alkylated secondary alcohols. This catalyst demonstrated excellent durability during successive recycling without leaching of Ru which is ascribed to the strong binding of the pincer ligands to the metal ions.

Aerobic oxidation of primary alcohols in the presence of activated secondary alcohols

2005 ◽  
Vol 46 (5) ◽  
pp. 783-786 ◽  
Author(s):  
Hiromichi Egami ◽  
Hideki Shimizu ◽  
Tsutomu Katsuki
Keyword(s):  
Aerobic Oxidation ◽  
Secondary Alcohols ◽  
Primary Alcohols

Alkoxylation of 2,3-dialkylindoles utilizing iodosobenzene diacetate

1980 ◽  
Vol 58 (15) ◽  
pp. 1589-1591 ◽  
Author(s):  
Dennis V. C. Awangz ◽  
André Vincent
Keyword(s):  
Simple Procedure ◽  
Secondary Alcohols ◽  
Complex Products ◽  
Tert Butanol

Iodosobenzene diacetate has been employed in the development of a simple procedure for the production of 3-alkoxyindolenines from 2,3-disubstituted indoles, by treatment of the indoles with the reagent in alcoholic solvent.Primary and secondary alkoxy functions have been incorporated at the β-site of 2,3-dimethylindole but the reaction with tert-butanol leads to other complex products. Good yields of 9-n-alkoxy-9H-reserpines have been realised but no reaction is observed in secondary alcohols.

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