title: In vitro reaction of barbiturates with formaldehyde.
abstract: Barbiturates are widely used as sedatives, hypnotics, and antiepileptics, and, when coupled with their narrow therapeutic index, the probability that their use will result in accidental or intentional death is significant. When barbiturates are implicated in a murder or suicide, analysis for their presence is often required. Under certain conditions, barbiturates are quite stable, but conditions found in vivo immediately after death or after embalming may promote barbiturate decomposition. If extensive decomposition occurs, analysis for them may be difficult or impossible. Here, the stability of three representative barbiturates, under conditions that model those likely to prevail in vivo shortly after death and after embalming, have been studied. Solutions of phenobarbital were found to slowly decompose in water over the pH range of approximately 3.5 to 9.5. More rapid decomposition occurred at higher pH, and 2-phenylbutyric acid was the main decomposition product. Formaldehyde (5-20%) accelerated the decomposition rate 3-10-fold such that phenobarbital decomposition could be complete after 30 days. In contrast, pentobarbital decomposed roughly 10 times more slowly and secobarbital did not detectably decompose under any of the conditions studied. Thus, certain barbiturates may partially or completely decompose in vivo after death, especially after embalming, and thus analysis for them may lead to false negatives. However, this work shows that analysis for the parent barbiturate or its predicted decomposition product may provide data that will reduce the likelihood of false negatives.
authors.affiliation: West Virginia University, School of Pharmacy, Basic Pharmaceutical Sciences, Morgantown 26506, USA. pgannett@hsc.wvu.edu
authors.forename: P M
authors.initials: PM
authors.lastname: Gannett
authors.forename: J R
authors.initials: JR
authors.lastname: Daft
authors.forename: D
authors.initials: D
authors.lastname: James
authors.forename: B
authors.initials: B
authors.lastname: Rybeck
authors.forename: J B
authors.initials: JB
authors.lastname: Knopp
authors.forename: T S
authors.initials: TS
authors.lastname: Tracy
mesh_terms: D001463:Barbiturates / Q000032:analysis / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D004615:Embalming; D005404:Fixatives / Q000737:chemistry*; D005554:Forensic Medicine; D005557:Formaldehyde / Q000737:chemistry*; D006801:Humans; D066298:In Vitro Techniques; D011180:Postmortem Changes; D013048:Specimen Handling
chemical_list: D001463:Barbiturates; D005404:Fixatives; D005557:Formaldehyde