Aromatic amines are known to undergo covalent binding with humic substances in the environment. Although previous studies have examined reaction conditions and proposed mechanisms, there has been no direct spectroscopic evidence for the covalent binding of the amines to the functional groups in humic substances. In order to further elucidate the reaction mechanisms, the Suwannee River and IHSS soil fulvic and humic acids were reacted with 15 N-labeled aniline at pH 6 and analyzed using 15 N NMR spectrometry. Aniline underwent nucleophilic addition reactions with the quinone and other carbonyl groups in the samples and became incorporated in the form of anilinohydroquinone, anilinoquinone, anilide, imine, and heterocyclic nitrogen, the latter comprising 50% or more of the bound amine. The anilide and anilinohydroquinone nitrogens were determined to be susceptible to chemical exchange by ammonia. In the case of Suwannee River fulvic acid, reaction under anoxic conditions and pretreatment with sodium borohydride or hydroxylamine prior to reaction under oxic conditions resulted in a decrease in the proportion of anilinohydroquinone nitrogen incorporated. The relative decrease in the incorporation of anilinohydroquinone nitrogen with respect to anilinoquinone nitrogen under anoxic conditions suggested that inter-or intramolecular redox reactions accompanied the nucleophilic addition reactions.

Phenyllithium forms a mixture of tetramer and dimer in ether. Complete conversion to dimeric solvates is achieved by the addition of THF, dioxolane, DME, or TMEDA in near stoichiometric amounts. The addition of 2,5-dimethyltetrahydrofuran favors dimer, but tetramer is still detectable at 14 equiv of cosolvent. PMDTA converts PhLi to monomer in ether. In THF, PhLi is a mixture of dimer and monomer. Addition of TMEDA forms a series of complexes, but the dimer/monomer ratio is essentially unaffected. PMDTA and HMPA form monomeric PhLi stoichiometrically. HMTTA and DMPU also result in monomer formation but several equiv are required. 12-Crown-4 shows no spectroscopically detectable complexation of PhLi in THF. All of the cosolvents tested increase the reactivity of PhLi in THF in a test metalation reaction:  HMPA and 12-crown-4 show the largest effects, PMDTA is intermediate, and HMTTA and TMEDA result in the least activation. In two selectivity tests, HMPA and 12-crown-4 show a substantially lower selectivity than the other cosolvents. We postulate that a contribution from a highly reactive separated ion pair (SIP) intermediate is responsible for the lower selectivity.

Chelation and aggregation in phenyllithium reagents with potential 6- and 7-ring chelating amine (2, 3) and 5-, 6-, and 7-ring chelating ether (4, 5, 6) ortho substituents have been examined utilizing variable temperature (6)Li and (13)C NMR spectroscopy, (6)Li and (15)N isotope labeling, and the effects of solvent additives. The 5- and 6-ring ether chelates (4, 5) compete well with THF, but the 6-ring amine chelate (2) barely does, and 7-ring amine chelate (3) does not. Compared to model compounds (e.g., 2-ethylphenyllithium 7), which are largely monomeric in THF, the chelated compounds all show enhanced dimerization (as measured by K = [D]/[M](2)) by factors ranging from 40 (for 6) to more than 200 000 (for 4 and 5). Chelation isomers are seen for the dimers of 5 and 6, but a chelate structure could be assigned only for 2-(2-dimethylaminoethyl)phenyllithium (2), which has an A-type structure (both amino groups chelated to the same lithium in the dimer) based on NMR coupling in the (15)N, (6)Li labeled compound. Unlike the dimer, the monomer of 2 is not detectably chelated. With the exception of 2-(methoxymethyl)phenyllithium (4), which forms an open dimer (12) and a pentacoordinate monomer (13), the lithium reagents all form monomeric nonchelated adducts with PMDTA.

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.