Ask them questions about the product or service. If they are enthusiastic and helpful, that will be an indicator that the company is a good place to work. If they don't respond, or forward you to marketing or sales, that tells you something else about the company.
After the initial contact, you might then ask questions about the company in general. Something like: we like the product, but are unsure if the company will be around in a year, etc. At that point the developer might just give you the standard company line, or might be more forth coming.