Intramolecular carbenoid insertions : the reactions of [alpha]-diazoketones derived from furanyl, thienyl, benzofuranyl and benzothienyl acetic acids with rhodium (II) acetate /

A number of synthetically useful ring systems can be prepared via the intramolecular insertion of a metal-stabilized carbenoid into a heteroaromatic systems. The chemical outcome of these reactions are dependent not only on the nature of the heteroatom but also on the length of the aliphatic tether linking the carbenoid moiety with the aromatic fragment. Our work with furanyl and thienyl systems containing a single methylene tether have allowed for some rather atypical chemistry. For example, treatment of l-diazo-3-(2-thienyl)-2-propanone (6) with catalytic rhodium (II) acetate yields 5,6- dihydro-4^-cyclopenta[Z>]thiophen-5-one (3) while, the isomeric l-diazo-3-(3-thienyl)-2- propanone(15) gives a spiro-disulphide (20). Novel chemistry was also exhibited in the analogous furanyl systems. While treatment of l-diazo-3-(3-furanyl)-2-propanone (52) with Rh2(OAc)4 resulted in the expected 2-(4-Oxo-2-cyclopentenyliden)acetaldehyde (54), isomeric l-diazo-3-(2- furanyl)-2-propanone (8) undergoes vinylogous Wolff rearrangement to give a mixture of 6a-methyl-2,3,3a,6a-tetrahydrofuro[2,i-^>]furan-2-one (44) and 2-(2-methyl-3-furyl)acetic acid (43). Rhodium acetate catalyzed decomposition of l-diazo-3-(3-benzofuranyl)-2- propanone (84) and l-diazo-3-(2-benzofuranyl)-2-propanone (69)also allows for vinylogous Wolff rearrangement, a chemistry unseen in benzofuranyl systems with longer tethers. A number of interesting products were isolated from the trapping of intermediate ketenes. Decomposition of l-diazo-3-(3-benzothienyl)-2-propanone (100) resulted in the formation of 2,3-dihydro-l//-benzo[^]cyclopenta[^thiophen-2-one (102). However, in addition to (102), a dimer was also generated from the decomposition of l-diazo-3-(2- benzothienyl)-2-propanone (109). The insight into the mechanistic underpinnings of the above reactions are provided by molecular modeling at a PM3 level.

The 21-dehydroxglation of corticosteroids of Eubacterium lentum and the dehalogenation of 4-chlorobenzoic acid by 4-chlorobenzoate dehalogenase

Two enzyme mechanisms were investigated: the 21-dehydroxylation of corticosteroids by Eubacterium lentum and the dehalogenation of 4-chlorobenzoic acid by Pseudomonas sp. CBS 3. , Chemical and enzymic methods of reduction of 21-oxo steroids were used to generate C-21-d1 compounds of tetrahydrodeoxycorticosterone, with both predominant stereochemistries. It was found that during the dehydroxylation the pro-S hydrogen at the C-21 position was lost preferentially. This suggests that the enzyme removes the pro-S hydrogen during binding to the active site as the ene-diol. To study the hydrolytic replacement of chlorine by hydroxyl , p-chlorobenzoic acid-d4 was prepared and sent to Germany for an ~ncubation with an enzyme preparation of 4-Chlorobenzo~te Dehalogenase. Results suggests the possible loss of deuterium during the conversion of p-chlorobenzoate to p-hydroxybenzoate, from all four ring positions. Many methods of preparing the control compound p-hydroxybenzoic acid-d4 were investigated.

The Badger: Vol. 2 Issue 3

The Badger newspaper gets a new look in this fall issue.

Investigations of 2-alkyl-3-methoxypyrazines in three ladybug species and wine /

Investigations of 2-alkyl-3-methoxypyrazines (2-isopropyl-3-methoxypyra2ine, 2- secbutyl-3-methoxypyrazine and 2-isobutyl-3-niethoxypyrazine) in ladybug species {Coleoptera: Coccinellidae) and wine samples have been conducted. Headspace sampling coupled with gas chromatography-mass spectrometry was used to determine amounts of 2-alkyl-3-methoxypyra2ines in the ladybug species. Hippodamia convergens had the highest amount of alkybnethoxypyrazines, followed by Harmoma axyridis and the least in Coccinella septempunctata. Using a solvent extraction method, the precoccinelline alkaloid was found present in Hippodamia convergens and Coccinella septempunctata but not Harmonia axyridis. Steam distillation followed by a soHd phase extraction method as a sample preparation technique, enhanced detection while the isotope dilution method afforded accurate quantitation of the alkyknethoxypyrazines in the wine samples. Both ladybug-tainted and commercial wine samples were found to contain the 2- alkyl-3-methoxypyrazines. Wine samples prepared in 2001 generally contained higher levels than the corresponding 2003 samples. Levels of the 2-alkyl-3-methoxypyrazines found in the commercial wines ranged from a minimum value of 6 ng/L to 260 ±10 ng/L. Analyses revealed that for both ladybug species and wine samples, the 2- isopropyl-3-methoxypyrazine had the highest concentration, followed by 2-isobutyl- 3-methoxypyrazine and the least being the 2-secbutyl-3-methoxypyrazine. Possible contamination of the wine samples by ladybugs is thoroughly discussed. Furthermore, attempts to remove or reduce the levels of the alkylmethoxypyrazines with molecularly imprinted polymers from wine samples are presented in detail.

Second Welland Canal - Book 1, Survey Map 11 - St. Catharines and Locks 3 and 4

Survey map of the Second Welland Canal created by the Welland Canal Company showing the Town of St. Catharines. Identified structures associated with the Canal include Lock 3 and its Lock House, Lock 4 and its Lock House, Hydraulic Race, and a floating tow path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Geneva Street, Ontario Street, St. Paul Street, and Merritville Road), Lincoln Mills and its Store House, T. M. Merritt's Store House, Cooper Shop, L. Shickluna's Dry Dock, Peter McGill's Grist Mill, J. Flint's Saw Factory, T. Hosteter's Gristing Mill, J. Dougan Builder's shop or office, Norris and Nelson Mill, G. N. Oil Foundry and its Machine Shop and Boiler, a barrel shed, woolen factory, Estate of P. Nihen (or T. Nihan), Norris and Nelson's Wharf, the W. C. Office, and structures (possibly houses) or small properties belonging to T. Adams, and A. K. Boomer. Properties and property owners of note are: Concession 6 Lots 16, 17, and 18, Concession 7 Lots 16, 17, and 18, Alva Dittrick, James R. Benson, W. B. Robinson, and C. Phelps.

Synthesis of 3', 5'-cyclic diguanylic acid (c-di-GMP) analogues

In the past few years, interest in signaling networks involving 3ʹ, 5ʹ -cyclic diguanylic acid (c-di-GMP) has increased dramatically. Evidence started to emerge that connects c-di-GMP to the regulation of a range of biological processes in bacteria, such as bacterial biofilm formation, virulence, extracellular polysaccharide synthesis, however, much remains to be explored in the signaling pathways that involve this secondary messenger. This molecule has also been shown to be a very powerful immunostimulating agent and potent mucosal vaccine adjuvant.

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month of Sept. 1854, signed by S.D. Woodruff, Oct. 1854.

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines during the month ending Oct. 31, 1854.

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month of Oct. 1854

Estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month of Oct. 1854, signed by S.D. Woodruff, Nov. 1854.

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month ending Dec. 1, 1854

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month ending Dec. 1, 1854, signed by S.D. Woodruff, Jan. 1855.

An estimate of work done by Messrs. Brown and McDonell, contractors on sections 1, 2 and 3 ending at St. Catharines for the months of April and May 1855

Scrap of paper that has been burned almost completely. Only the header of the document is intact. It is an estimate of work done by Messrs. Brown and McDonell, contractors on sections 1, 2 and 3 ending at St. Catharines for the months of April and May 1855.

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month of Oct., 1855. This document is water damaged and full of holes. The list of prices is almost completely illegible. The document is signed by S.D. Woodruff, Nov. 1855.

Schedule of prices for Brown and McDonell, contractors, for sections 1, 2 and 3 of the Port Dalhousie Thorold Railway

Schedule of prices for Brown and McDonell, contractors, for sections 1, 2 and 3 of the Port Dalhousie Thorold Railway (1 page, handwritten), Sept. 24, 1856.

County of Welland estimate (copy) of work done on sections 2 and 3 of the tap drain at Marshville by George Stanford

County of Welland estimate (copy) of work done on sections 2 and 3 of the tap drain at Marshville by George Stanford, signed by S.D. Woodruff. Estimate no.1, July, 1856.

County of Welland estimate (copy) of work done on sections 2 and 3 of the tap drain at Marshville by George Stanford

County of Welland estimate (copy) of work done on sections 2 and 3 of the tap drain at Marshville by George Stanford, signed by S.D. Woodruff. Estimate no.2, Oct., 1856.