> 1) are pyridine fumes dangerous?
Before you reach toxic doses you have already left the house... pyridine has a HIGHLY unpleasant odor... Triethylamine is a good substitute.
> 2) to co-distill one would dissolve the 4-acetoxy-indole residue in tolulene then strip all the tolulene off? or does the 4-acetoxy-indole boil first leaving heavier impurities in the tolulene?
I think it means to add fresh toluene to remove traces of pyridine.
I would suggest the following: acetanhydrid, triethylamine (maybe org. solvent), let react, add water to destroy excess acetanhydride (or distill most of it off), basify, partition between water and organic solvent (to remove the acetic acid), wash again with acidic water (to remove the organic base), wash to neutrality with water, dry (MgSO4), and evaporate. Then vacuum-distill the acetoxy-indole.
> 3) in the ace-dmt ref on rhodium's page 4-benzyloxy-indole is plugged into shulgin's dmt synth via oxalyl chloride in Et2O, then dimethylamine in Et2O to indol-3-yl-N,N-dimethylglyoxylamide, then after reduction with LAH in THF to 4-benzyloxy-dmt converted to 4-acetoxy-dmt. can 4-acetoxy-indole be substituted initially?
Yes.
> equally true for dimethylamine, diethylamine, and diisopropylamine?
Yes. Yes. Possibly (diisopropylamine is sterically hindered, the reaction conditions are probably much, much harsher.)
I would suggest a view into the original literature (which can be found under
http://www.fortunecity.com/westwood/storey/116
)