To make the make the pineapple chile syrup, place the water and the sugar in a medium saucepan. Stir the mixture together and bring to a simmer over medium heat. Stir occasionally until the sugar dissolves. Add the pineapple chunks (along with any accumulated juice) and the jalapeno chile to the syrup mixture and stir well. Bring the mixture back to a simmer. Remove from heat and cover. Allow to steep until mixture is completely cool. Strain through a fine mesh strainer, gently pressing on the pineapple to extract any remaining juice. Store in the refrigerator
For the rim mixture, stir all ingredients together and place in a shallow bowl or saucer.
To assemble the cocktail, use a piece of pineapple to moisten the rim of an old-fashioned glass. Set the rim into the rim mixture and set aside. Measure first 4 ingredients and place in a cocktail shaker. Fill the shaker with ice and shake vigorously for 45 to 60 seconds. Strain cocktail into the prepared glasses. Garnish with pineapple wedge and jalapeno slice, if desired.