Biomedical subjects

W S Goldenberg

Publications and source records attributed to W S Goldenberg.

3 recordsLinked to original sources

PubMed2001

Amine-chelated aryllithium reagents--structure and dynamics.

Multinuclear NMR studies of five-membered-ring amine chelated aryllithium reagents 2-lithio-N,N-dimethylbenzylamine (1), the diethylamine and diisopropylamino analogues (2, 3), and the o-methoxy analogue (4), isotopically enriched in (6)Li and (15)N, have provided a detailed picture of the solution structures in ethereal solvents (usually in mixtures of THF and dimethyl ether, ether, and 2,5-dimethyltetrahydrofuran). The effect of cosolvents such as TMEDA, PMDTA, and HMPA has also been determined. All compounds are strongly chelated, and the chelation is not disrupted by these cosolvents. Reagents 1, 2, and 3 are dimeric in solvents containing a large fraction of THF. Below -120 degrees C, three chelation isomers of the dimers are detectable by NMR spectroscopy: one (A) with both nitrogens coordinated to one lithium of the dimer, and two (B and C) in which each lithium bears one chelating group. Dynamic NMR studies have provided rates and activation energies for the interconversion of the 1-A, 1-B, and 1-C isomers. They interconvert either by simple ring rotation, which interconverts B and C, or by amine decoordination (probably associative, DeltaG(++)(-93) = 8.5 kcal/mol), which can interconvert all of the isomers. The dimers of 1 are thermodynamically more stable than those of model systems such as phenyllithium, o-tolyllithium, or 2-isoamylphenyllithium (5, DeltaDeltaG > or = 3.3 kcal/mol). They are not detectably deaggregated by TMEDA or PMDTA, although HMPA causes partial deaggregation. The dimers are also more robust kinetically with rates of interaggregate exchange, measured by DNMR line shape analysis of the C-Li signal, orders of magnitude smaller than those of models (DeltaDeltaG(++) > or = 4.4 kcal/mol). Similarly, the mixed dimer of 1 and phenyllithium, 13, is kinetically more stable than the phenyllithium dimer by >2.2 kcal/mol. X-ray crystal structures of the TMEDA solvate of 1-A and the THF solvate of 3-B showed them to be dimeric and chelated in the solid state as well. Compound 4, which has a methoxy group ortho to the C-Li group, differs from the others in being only partially dimeric in THF, presumably for steric reasons. This compound is fully deaggregated by 1 equiv of HMPA. Excess HMPA leads to the formation of ca. 15% of a triple ion (4-T) in which both nitrogens appear to be chelated to the central lithium.

Journal Article↗

PubMed2001

Chelated aryllithium reagents: ring size and chelating group effects.

[figure: see text] Chelation and aggregation in phenyllithium reagents with potential 5-, 6-, and 7-ring chelating ether and amine ortho substituents have been examined utilizing variable-temperature 6Li and 13C NMR spectroscopy, 6Li and 15N isotope labeling, and the effects of solvent additives. Both ether and amine form strong 5-ring chelates; 6-ring ether chelates compete well with THF, but 6-ring amine chelates barely do, and 7-ring amine chelates do not. o-Methoxymethylphenyllithium (4) forms an open dimer (9) and a pentacoordinate monomer with PMDTA (10).

Journal Article↗

PubMed2000

Too hot to handle: an unusual exposure of HDI in specialty painters.

BACKGROUND: Hexamethylene Diisocyanate (HDI) is a color stable aliphatic isocyanate that is used in specialty paints as a hardener. Due to the lower vapor pressure of its commercial biuret form, it is considered a relatively "safe" isocyanate from an exposure standpoint. This case series reports on an unusual toxic exposure to HDI. Between November 1993 and May 1994, seven specialty painters and one boiler maker who were working at three different power plants were examined at the Institute of Occupational and Environmental Health at West Virginia University. At their respective work sites, HDI was applied to the hot surfaces of boilers that were not shut down, and allowed sufficient time to cool. Consequently, these workers were exposed to volatile HDI and its thermal decomposition products. METHODS: All of these workers underwent a complete physical examination, spirometry, and methacholine challenge testing. RESULTS: All 8 workers complained of dyspnea, while 4 of the 8 also complained of rash. On examination 3 workers were methacholine challenge positive and 2 had persistent rash. At follow-up 4 years later, 5 workers still had to use inhalation medication and one had progressive asthma and dermatitis. All 8 workers, by the time of the follow-up, had gone through economic and occupational changes. CONCLUSIONS: This case series reports on an unusual exposure to HDI. It is unusual in that: 1) There were two simultaneous sentinel cases with two different Material Safety Data Sheets (MSDS) for the same product, 2) Exposure was to volatile HDI and its decomposition products and 3) Hazardous conditions of exposure occurred at three different sites.

Adult↗