Modifying alkylzinc reactivity with 2,2 '-dipyridylamide : activation of tBu-Zn bonds for para-alkylation of benzophenone

Undercover agent: Masquerading as a simple donor-acceptor complex (1), sodium amide substoichiometrically activates tBuZn for the challenging 1,6-addition of a tert-butyl group to benzophenone. In contrast, the nonactivated tBuZn is ineffectual

2-Hexadecynoic Acid

The hitherto undescribed 2-hexadecynoic acid (III) was prepared by the following route. Dodecylmagnesium bromide was reacted with 2,3-dibromopropene to give 2~:bromop e ntadecene (I) in 35 % yield. Refluxing the bromo compound I with freshly prepared sodium amide in xylene gave pentadecyne(II) in 49 .1 % yiel

2-Hexadecynoic Acid

The hitherto undescribed 2-hexadecynoic acid (III) was prepared by the following route. Dodecylmagnesium bromide was reacted with 2,3-dibromopropene to give 2~:bromop e ntadecene (I) in 35 % yield. Refluxing the bromo compound I with freshly prepared sodium amide in xylene gave pentadecyne(II) in 49 .1 % yiel

Synthesis of perfluoroalkylene dianilines

The objective of this contrast was to optimize and scale-up the synthesis of 2,2-bis(4-aminophenyl)-hexafluoropropane and 1,3-bis(4-aminophenyl)hexafluoropropane, as well as to explore avenues to other perfluoroalkyl-bridged dianilines. Routes other than Friedel-Crafts reaction leading to 2,2-bis(4-aminophenyl)hexafluoropropane were investigated. The processes utilizing bisphenol-AF were all unsuccessful; reactions aimed at the production of 4-(hexafluoro-2-halo-isopropyl)aniline from the hydroxyl intermediate failed to yield the desired products. Tailoring the conditions of the Friedel-Crafts reaction of 4-(hexafluoro-2-hydroxyisopropyl)aniline, aniline, and aluminum chloride by using hydrochloride salts and selecting optimum reagent ratios, reaction times, and temperature resulted in approx. 20% yield of pure crystallized 2,2-bis(4-aminophenyl)hexafluoropropane in 0.2 mole reaction batches. Yields up to approx. 40% were realized in small, approx. 0.01 mole, batches. The synthesis of 1,3-bis(4-aminophenyl)hexafluoropropane starting with perfluoroglutarimidine was reinvestigated. The yield of the 4-step reaction sequence giving 1,3-bis(4-acetamidophenyl)hexafluoropropane was raised to 44%. The yield of the subsequent hydrolysis process was improved by a factor of approx. 2. Approaches to prepare other perfluoroalkyl-bridged dianilines were unsuccessful. Reactions reported to proceed readily with trifluoromethyl substituents failed when longer chain perfluoroalkyl groups were employed

A Perspective Distilled from Seventy Years of Research

Physical organic chemistry might be regarded as officially recognized as a distinct discipline through the publication of L. P. Hammett’s book of that title, although substantial earlier work can be traced back to the turn of the 20th century. Many of the instrumental tools that helped the discipline develop in so many different ways began to appear in the late thirties and during World War II and were soon built to be increasingly operated in the “hands-on” mode. This development became very popular in academia, where instruments are not operated for you by an expert, but even if you are an undergraduate, you can more or less be the expert yourself and take many varieties of data on instruments usually available on a 24 h basis. It has been my privilege and joy to begin research in chemistry just as these waves of change began to grow and to savor the great contribution that the new methods, such as measurement of 14C, UV−vis, IR, NMR, and hands-on use of computers, made in facilitating our research programs at MIT and later at Caltech. Among those programs, which will be discussed, were 14C tracing of carbocation rearrangements and benzyne formation, electrical effects of substituents, Grignard reagents, synthesis of small-ring compounds, (2 + 2) cycloaddition reactions of halogenated ethylenes, assisting in development of ^(19)F, ^(13)C, and ^(15)N NMR for conformational analysis, other structural, kinetic, and tracer studies, as well as helping through textbooks to bring Hückel MO theory and the elements of NMR to familiarity for organic chemists. From the very beginning of my research career, I have been the beneficiary of personal mentoring which has been very crucial to my success in research and is an important theme in what follows

Synthesis of Some Benzimidazole-substituted Benzotriazoles

2-Alkylsubstituted benzimidazoles (3a–h) were prepared from the acid-catalyzed reaction of 4-methyl-1,2-phenylenediamine with corresponding carboxylic acids. Addition of these benzimidazoles to N-chloromethylbenzotriazole in the presence of sodium amide under reflux conditions gave the novel benzimidazole-substituted benzotriazoles (5a–f). IR and 1HNMR spectroscopy and elemental analysis were used for the identification of these compounds.Keywords: Phenylenediamine, benzimidazole, benzotriazol

Synthetic utility and reactivity of N-alkynylazoles

textThe chemistry of N-alkynylazoles is a newly emerging area of chemistry with particular interest in heterocycle synthesis. Synthetic preparations of this class of molecule have shown an increasing presence in literature, however, the synthetic utility of this class of molecule remains underexplored. Herein, it is shown that N-alkynlazoles are a versatile synthetic intermediate and may have utility as covalent modifiers of cysteine residues in polypeptides.Pharmaceutical Science

Multistep self-assembly of heteroleptic magnesium and sodium-magnesium benzamidinate complexes

Reaction of the magnesium bis-alkyl Mg(CH2SiMe3)(2) and the sodium amide NaHMDS (where HMDS = N(SiMe3)(2)) with benzonitrile yields the homometallic heteroleptic complex [PhC(NSiMe3)(2)Mg{mu-NC(CH2SiMe3)Ph}](2) (1). It appears that at least six independent reactions must have occurred in this one-pot reaction to arrive at this mixed benzamidinate ketimido product. Two benzonitrile solvated derivatives of Mg(CH2SiMe3)(2) (5a and 5b) have been synthesized, with 5a crystallographically characterized as a centrosymmetric (MgC)(2) cyclodimer. When, the components of 5a are allowed to react for longer, partial addition of the Mg-alkyl unit across the C N triple bond occurs to yield the trimeric species (Me3SiCH2)(2)Mg-3[mu-N=C(CH2SiMe3)Ph](4)center dot 2N CPh (6), with bridging ketimido groups and terminal alkyl groups. Finally, using the same starting materials as that which produced 1, but altering their order of addition, a magnesium bis-alkyl unit is inserted into the Na-N bonds of a benzamidinate species to yield a new sodium magnesiate complex, PhC(NSiMe3)(2)Mg(mu-CH2SiMe3)(2)Na center dot 2TMEDA (7). The formation of 7 represents a novel (insertion) route to mixed-metal species of this kind and is the first Such example to contain a bidentate terminal anion attached to the divalent metal center. All new species are characterized by H-1 and C-13 NMR spectroscopy and where appropriate by IR spectroscopy. The solid-state structures of complexes 1, 5a, and 7 have also been determined and are disclosed within

The madelung synthesis of dihydro-1H-pyrrolo- and tetrahydropyrido[1,2-a]- indoles under mild conditions

Benzeneacetonitriles substituted with lactam moieties in the ortho-position cyclize under the influence of a base, dependent on the ring-size of the lactam function, to dihydropyrrolo-, tetrahydropyrido[1,2-a]indole or dihydro-1-benzazepin derivatives, respectively