you can try using the VALUE function to get the decimal value from the currency field before passing it to the webservice method.
Example:
We want to pass decimal value of Opportunity Amount. Then we use below code in custom button to pass decimal value to web-service.
{!REQUIRESCRIPT("/soap/ajax/10.0/connection.js")}
{!REQUIRESCRIPT("/soap/ajax/10.0/apex.js")}
var amt = {!VALUE(TEXT(Opportunity.Amount))};
var retVal = sforce.apex.execute("WSclassname", "WSmethod", {oppAmt:amt});
alert (retVal) ;
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