(endo)-5-(2-haloethyl)-2-norbornene. A new radical probe.

(endo)-5-(2-haloethyl)-2-norbornenes have been synthesized, and their corresponding radicals generated by reaction with sodium, magnesium, sodium naphthalenide and tri-n-butyltin hydride in the presence of AIBN to produce both straight chain and cyclized products. This probe cyclizes substantially faster than the often used 5-hexenyl halide probes.     

Linus Carl Pauling - 28. 2. 1901 - 17.8. 1994

Das Jahr 1939 steht, wie in der Geschichte der Menschheit, auch in der der Chemie wie eine Zeitenwende: Während von Berlin aus in der Welt die Lichter ausgelöscht wurden, erschien in New York ein Buch von mäßigem Umfang: Linus Pauling: „The Nature of the Chemical Bond and the Structure of Molecules and Crystals - An Introduction to Modern Structural Chemistry”︁. Man kann seit diesem fokussierenden Genieblitz tatsächlich die Chemie in ihren weitesten Ausstrahlungen als Zeit vor (B. P.) und nach Pauling (A. P.) zählen, denn dieses Buch hatte einen ungeheuren Einfluß auf alles, das chemisch ist - und das ist alles Tote und Lebende, weil es durch chemische Bindungen in Form und im Raum gehalten wird. Und es ist nicht ein Zufallsstreich, sondern das Ergebnis einer phänomenalen Zusammenschau und einer, durch Gespür für das, was die Natur zusammenhält, zielvoll gelenkten, von Intuition beflügelten und seismorgraphisch alle Anregungen aufnehmenden, ungeheuer optimistischen geistigen und experimentellen Arbeit eines Mannes, der zugleich die Phantasie hatte, die neuen Vorstellungen auf viele in den Kulissen stehende Fragen anzuwenden, so daß wir heute reflexmäßig die Vorgänge in uns und um uns herum als Yin/Yang(Paß)-Kommunikation zwischen Atomen, Molekülen und höher strukturierten Verbänden, Organisationen interpretieren.     

Pyridine-substituted hydroxythiophenes. IV. Preparation of 3- and 4-(2-, 3- and 4-pyridyl)-2-hydroxythiophenes

3-(2-, 3- and 4-Pyridyl)-2-methoxythiophenes have been prepared in good yields through the Pd(0)-cat-alyzed coupling of the three isomeric bromopyridines with 3-trimethylstannyl-2-methoxythiophene. This compound was prepared through halogen-metal exchange of 3-bromo-2-methoxythiophene followed by stannylation. 3-Bromo-2-methoxythiophene was prepared by dibromination and α-debromination of 2-methoxythiophen. Most attempts to demethylate 2-methoxy-3-pyridylthiophenes using a large variety of reagents failed, probably due to the instability and high reactivity of the desired 3-pyridyl-2-hydroxythiophene systems. Only 2-methoxy-3-(3-pyridyl)thiophene reacted with boron tribromide to give 3-(3-pyridyl)-3-thiolene-2-one, which only was stable in ether solution at ?20°. The attempted demethylation of 2-methoxy-3-(2-pyridyl)thiophene with trimethylsilane chloride/sodium iodide in refluxing acetonitrile led to a dimer. Demethylation of the 2-methoxy-3-pyridylthiophenes with dibenzyl diselenide and sodium borohydride gave 3-pyridylthiophan-2-ones. A number of other routes to prepare 3-pyridyl-2-hydroxythiophenes were also explored, but none of them gave the desired compounds. On the other hand, the 4-(2-, 3-, and 4-pyridyl)-2-hydroxythiophene systems could easily be prepared by hydrogen peroxide oxidation of the corresponding 4-pyridyl-2-thiopheneboronic esters, which were obtained from 2-bromo-4-pyridylthiophenes by halogen-metal exchange followed by reaction with ethyl borate. The 2-bromo-4-pyridylthiophenes were prepared by dibromination of the known 3-pyridylthiophenes to the 2,5-dibromo derivatives, and removal of the 2-bromine by halogen-metal exchange at ?100°, followed by hydrolysis. The ¹H nmr and ir spectroscopic investigations show that these quite stable 2-hydroxythiophene systems exist exclusively in the 4-pyridyl-3-thiolen-2-one forms.     

Pyridine-substituted hydroxythiophenes. V. Preparation of 5-(2-, 3-and 4-pyridyl)-2-hydroxythiophenes

5-(2-, 3- and 4-Pyridyl)-2-t-butoxythiophenes have been prepared in very good yields by Pd(0) catalyzed cross-coupling of the three isomeric bromopyridines with 5-trimethylstannyl-2-t-butoxythiophene derived from 2-bromothiophene via 2-t-butoxythiophene. Dealkylation of 5-(2-, 3- and 4-pyridyl)-2-t-but-oxythiophenes with boron trifluoride etherate in dichloromethane at room temperature led to predominant formation of rearranged products, 5-(2- and 3-pyridyl)-3-t-butyl-3-thiolene-2-ones, together with a small amount of 5-(2- and 3-pyridyl)-2-hydroxythiophenes as a mixture of two tautomeric keto forms in the case of the 2-pyridyl and the 3-pyridyl isomers, and exclusive formation of rearranged product in the case of the 4-pyridyl isomer. However, dealkylation of 2-methoxy-5-(2-, 3- and 4-pyridyl)thiophenes, prepared similarly to the 5-(2-, 3- and 4-pyridyl)-2-t-butoxythiophenes, with boron tribromide under the same reaction conditions as above resulted exclusively in the tautomeric mixture of 5-(2- and 3-pyridyl)-3-thiolene-2-ones and 5-(2- and 3-pyridyl)-4-thiolene-2-ones in the case of the 2-pyridyl and 3-pyridyl isomers. In the case of the 4-pyridyl isomer polymerization took place.     

2-Oxocephems. II. - synthesis of 2-oxocephalexin from hetacillin

2-Oxocephalexin 4 , a very labile representative of the novel group of 2-oxocephem-4-carboxylic acids, has been synthesized from hetacillin.     

Nitroimidazoles. VI. Syntheses of 1-methyl-2-(1,3,4-thiadiazol-2-yl)-5-nitroimidazole and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-5-nitroimidazole

Starting from readily available 1-methyl-5-nitroimidazole-2-carboxylic acid hydrazide (1), 1-methyl-2-(1,3,4-thiadiazol-2-yl)-5-nitroimidazole (4) and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-5-nitroimidazole (10) were prepared. The reaction of 1 with formic acid gave 1-(1-methyl-5-nitroimidazole-2-carboxyl)-2-(formyl)hydrazine ( 8 ) in high yield. Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 4 in 50% yield. Reaction of compound 8 with phosphorus pentoxide afforded compound 10 in 60% yield.     

Reagents for new heteroannelation reactions III. 2-(Methylthio)-2-thiazoline

Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh     

Crystal structure of 3,3-dichloro-N-p-methoxyphenyl-4-(2-phenylstryl)-2-azetidinone.

3,3-Dichloro-N-p-methoxyphenyl-4-(2-phenylstryl)-2-azetidinone (C22H15Cl2NO2) was studied by X-Ray analysis, which indicated a monoclinic space group, P2(1)/c, with a = 9.619(5), b = 13.879(4), c = 14.161(5)A, beta = 100.16(3)degrees, V = 1860.8(13)A3, Z = 4, Dc = 1.414 g cm(-3), micro(Mo Kalpha) = 0.366 mm(-1) and F000 = 816. The structure was solved by direct methods and refined to R = 0.041 for 4026 reflections [I > 2sigma(I). The beta-lactam ring (2-azetidinone) has antimicrobial affects. The substituents of the methoxyphenyl and phenyl substituents do not change the activity property of the beta-lactam ring, and the activity properties depend on the planarity of the beta-lactam ring.     

3-Bromo-2-(tert-butylsulfonyl)-1-propene. A multi-coupling reagent. Part 2. <1

3-bromo-2-(tert-butylsulfonyl)-1-propene 1 reacts in good yields with various electrophiles (aldehydes, ketones, nitriles and alkynes) in the presence of zinc metal to give unsaturated sulfones of type 4. These compounds can further react with soft or hard nucleophiles (alkyl-, vinyl-, aryllithium compounds, a nitroparaffin or dimethylmalonate) to yield highly functionnalized sulfones of type 5 which can be readily transformed into enones or into a dienone. Thus sulfone 1 is a versatile multi-coupling reagent which is synthetically equivalent to the $\text{a}{}^2\text{a}{}^{\mathrm{2\prime }}$ synthon 8 and to the $\text{d}{}^2\text{d}{}^{\mathrm{2\prime }}$ synthons 9 and 10.     

2-Benzopyrylium salts. 24. Synthesis and reactions of 3-(2-methylenecarboxyaryl)-2-benzopyrylium salts with amines

5-Oxoniachrysene and N-methylisoquinolinium perchlorates and substituted 1-naphthylamines were synthesized on the basis of 1-R-3-(2-methylenecarboxyaryl)-2-benzopyrylium salts.See [1] for Communication 23.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 313–316, March, 1981.     

Tetrazoles. 42. 2-(4-Nitrophenyl)-5-functionally-substituted Tetrazoles

We have studied the reactions of 5-methylsulfonyl-2-(4-nitrophenyl)tetrazole with N- and O-nucleophiles. For the first time we show that in 2-(4-nitrophenyl)-5-phenoxytetrazole, the tetrazole ring is substituted when treated with phenoxide ion, 4-nitrodiphenyl ether being formed.     

Organoboron compounds Communication 409. 2-(2-thienyl)-1-boraadamantane pyridinate

Conclusions From 2-propargylthiophene and triallylborane, 2-(2-thienyl)-1-boraadmantane has been obtained.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1837–1841, August, 1984.