The DSS do include evidence that sin and shin were pronounced distinctly
by the 1st century CE, which certainly has a bearing on your theory by
restricting the date of the change you hypothesise. Ugaritic and the
Amarna Letters give evidence for the separate pronunciation of sin and
shin (well, I think they do, but I haven't checked) in languages closely
related to Hebrew at an earlier time, and disprove one older version of
your hypothesis according to which sin and shin were not separate in any
Semitic languages until a late date.
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