From Vox Graeca: A Guide to the Pronunciation of Classical Greek by W. Sidney Allen 1974 Cambridge.
The evidence thus seems conclusive that in 5 c. Attic φ, θ, χ represented plosives (as π, τ, κ) and NOT fricatives (as ς, or as φ, θ, χ in modern Greek). The continuation of the plosive pronunciation into a later period is shown by the fact that Latin renders Greek φ at first as a simple p, later as ph (e.g. Pilipus, Philippus), but never in classical Latin times as f, which would have been appropriate for a fricative pronunciation… However, there is no doubt that, as modern Greek shows, the aspirated plosives did eventually change to fricatives. Evidence is sometimes quoted which would suggest that the beginnings of such a change could be traced to the 2 c. B.C…. With one problematic exception the first clear evidence for a fricative pronunciation comes from the 1 c. A.D. in Pompeian spellings such as Dafne (= Δάφνη)… From the 2 c. A.D. the representation of φ by Latin f becomes common, and Latin grammarians have to give rules when to spell with f and when with ph… It may be that a scholarly pronunciation of φ, θ, χ as plosives continued for some time in the schools… There is even possibly some evidence that the plosive pronunciation continued in the schools up to the time when the Glagolitic alphabet was formed in the 9 c. for the writing of Old Church Slavonic.
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