Geminal halide hydrolysis: Difference between revisions
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'''Geminal halide hydrolysis''' is an [[organic reaction]]. The reactants are [[geminal]] [[halocarbon|dihalide]]s with a [[water]] molecule or a [[hydroxide]] [[ion]]. The reaction yields [[ketone]]s from [[Secondary (chemistry)|secondary]] halides<ref>{{cite journal|last1=Marvel|first1=C. S.|last2=Sperry|first2=W. M.|title=Benzophenone|journal=Organic Syntheses|date=1928|volume=8|page=26|doi=10.15227/orgsyn.008.0026}}</ref><ref>{{cite journal|last1=Pond|first1=F. J.|last2=O. P.|first2=Maxwell|last3=G. M.|first3=Norman|title=The Action of Sodium Methylate Upon Dibromides of Propenyl-Compounds and of Unsaturated Ketones|journal=Journal of the American Chemical Society|date=1899|volume=22|issue=11|pages=955–967|doi=10.1021/ja02061a002|url=https://zenodo.org/record/1428926}}</ref> or [[aldehyde]]s from [[Primary (chemistry)|primary]] halides.<ref>{{cite journal|last1=Bill|first1=J. C.|last2=Tarbell|first2=D. S.|title=o-Phthalaldehyde|journal=Organic Syntheses|date=1954|volume=34|page=82|doi=10.15227/orgsyn.034.0082}}</ref><ref>{{cite journal|last1=Buck|first1=Johannes S.|last2=Zimmermann|first2=F. J.|title=Protocatechualdehyde|journal=Organic Syntheses|date=1938|volume=18|page=75|doi=10.15227/orgsyn.018.0075}}</ref> | '''Geminal halide hydrolysis''' is an [[organic reaction]]. The reactants are [[geminal]] [[halocarbon|dihalide]]s with a [[water]] molecule or a [[hydroxide]] [[ion]]. The reaction yields [[ketone]]s from [[Secondary (chemistry)|secondary]] halides<ref>{{cite journal|last1=Marvel|first1=C. S.|last2=Sperry|first2=W. M.|title=Benzophenone|journal=Organic Syntheses|date=1928|volume=8|page=26|doi=10.15227/orgsyn.008.0026}}</ref><ref>{{cite journal|last1=Pond|first1=F. J.|last2=O. P.|first2=Maxwell|last3=G. M.|first3=Norman|title=The Action of Sodium Methylate Upon Dibromides of Propenyl-Compounds and of Unsaturated Ketones|journal=Journal of the American Chemical Society|date=1899|volume=22|issue=11|pages=955–967|doi=10.1021/ja02061a002|bibcode=1899JAChS..21..955P |url=https://zenodo.org/record/1428926}}</ref> or [[aldehyde]]s from [[Primary (chemistry)|primary]] halides.<ref>{{cite journal|last1=Bill|first1=J. C.|last2=Tarbell|first2=D. S.|title=o-Phthalaldehyde|journal=Organic Syntheses|date=1954|volume=34|page=82|doi=10.15227/orgsyn.034.0082}}</ref><ref>{{cite journal|last1=Buck|first1=Johannes S.|last2=Zimmermann|first2=F. J.|title=Protocatechualdehyde|journal=Organic Syntheses|date=1938|volume=18|page=75|doi=10.15227/orgsyn.018.0075}}</ref> | ||
==Reaction mechanism== | ==Reaction mechanism== | ||
Latest revision as of 10:24, 26 June 2025
Geminal halide hydrolysis is an organic reaction. The reactants are geminal dihalides with a water molecule or a hydroxide ion. The reaction yields ketones from secondary halides[1][2] or aldehydes from primary halides.[3][4]
Reaction mechanism
The first part of the reaction mechanism consists of an ordinary nucleophilic aliphatic substitution to produce a gem-halohydrin:
- RCH(Cl)2 + KOH RCH(OH)Cl + KCl
The remaining halide is a good leaving group and this enables the newly created hydroxy group to convert into a carbonyl group by expelling the halide:
- RCH(OH)Cl Rearrangement gives R-CHO + HCl
Variations
Other functional groups can undergo similar hydrolysis reactions. For instance, geminal trihalides (e.g. benzotrichloride) can be partially hydrolyzed to acyl halides (e.g. benzoyl chloride) in a similar way.[5] Further hydrolysis yields carboxylic acids.