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Rasha Nasha doesn't sell bottles to go, I'm pretty sure... Also, Starka is almost more like a whiskey than a vodka - distilled from rye, aged (with lime leaves in the barrel, if I remember right?) - and only twice distilled, so it's still got a bit of rye flavor, unlike vodkas which are distilled multiple times to the point they have no flavor at all. But there are some brands of "Starka" that are basically just neutral spirits with flavorings added, so unless you know the brands it's hard to know what you're getting.
I don't think I've ever seen it in NYC, but then I've never looked specifically for it. I think I remember seeing it in New Jersey at World of Liquors. Your best bet would be to check the various liquor stores out in "Little Poland" in Greenpoint, like foodwhisperer suggested - Dunne's Polemost Liquors and/or Save-Rite would probably be the best places to start. Also, Maspeth still has a large Polish population. Maybe check Maspeth Wines & Liquors. Unfortunately, you're probably just going to have to go out there and browse. Very few of (if any) of these little family-owned places have websites. You might want to post the same question on the "Outer Boroughs" board, maybe someone out there knows specifically or could look for you.
As a last resort after those, MAYBE the Russian liquor stores out in Brighton Beach - one often sees lots of brands you don't see anywhere else out there, and there's probably a half-dozen shops along the short stretch of Brighton Beach Ave east of Ocean Parkway - there's a Q stop right there, but it's a long way to go just to browse, and none of those shops (as in Greenpoint) have websites.
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Rasha Nasha Russian Vodka bar probably has it. 4 W 19th
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Nasha Rasha
4 W 19th St, New York, NY 10011 -
