14599-02-1

Basic information

• Product Name: Valine, N-benzoyl-3-chloro-, methyl ester
• CAS NO: 14599-02-1
• Molecular Formula: C13H16ClNO3
• Molecular Weight: 269.728
• Mol File: 14599-02-1.mol

Chemical Properties

• CAS DataBase Reference: Valine, N-benzoyl-3-chloro-, methyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: Valine, N-benzoyl-3-chloro-, methyl ester(14599-02-1)
• EPA Substance Registry System: Valine, N-benzoyl-3-chloro-, methyl ester(14599-02-1)

Safety Data

• Hazardous Substances Data: 14599-02-1(Hazardous Substances Data)

Upstream product

• 2280-28-6 3-hydroxy-DL-valine 
• 98-88-4 benzoyl chloride 
• 14598-96-0 DL-N-Benzyl-β-hydroxyvalin 
• 26924-22-1 methyl 2-benzamido-3-methylbut-2-enoate 
• 116222-73-2 N-benzoyl-N-chlorovaline methyl ester 
• 98517-03-4 N-benzoyl-2,3-dichlorovaline methyl ester 
• 14599-03-2 methyl 2-benzamido-3-methylbutanoate 
• 186581-53-3 diazomethane 
• 14598-98-2 α-benzoylamino-β-hydroxy-isovaleric acid 
• 98517-04-5 N-benzoyl-2,3-dibromovaline methyl ester 

Relevant articles and documents

REGIOSELECTIVE FORMATION OF AMIDOCARBOXY-SUBSTITUTED FREE RADICALS

Factors affecting the production of amidocarboxy-substituted free radicals have been investigated by examining reactions of derivatives of valine and sarcosine.Variations in the regioselectivity of reactions of these compounds are exemplified by the reactions of N-benzoylvaline methyl ester (4a) and N-benzoylsarcosine methyl ester (12a) with sulphuryl chloride and N-bromosuccinimide.Whereas the reaction of (4a) with sulphuryl chloride involves hydrogen-atom transfer from the β-position of (4a) with subsequent chlorine incorporation to give (4g), in direct contrast the reaction with N-bromosuccinimide proceeds via hydrogen-atom abstraction from the α-position of (4a) and yields the dibromide (4d).N-benzoylsarcosine methyl ester (12a), reacts with N-bromosuccinimide to give the α-bromosarcosine derivative (12b), whereas with sulphuryl chloride the product is the N-chloromethylglycine derivative (12c).These studies indicate that amidocarboxy-substituted radicals such as (3a) and (13) are considerably more stable than the tertiary alkyl radical (1a) and the amidosubstituted radical (14), respectively, but hydrogen-atom transfer reactions may afford the less stable products if electrophilic radicals are involved in the hydrogen-atom abstraction and if there is little development of radical character in the reaction transition state.

REGIOSELECTIVE CHLORINATION OF VALINE DERIVATIVES

Reaction of N-benzoylvaline methyl ester (5a) with sulphuryl chloride gave the β-chlorovaline derivative (6a) and lesser amounts of diastereoisomers of the γ-chlorovaline derivative (7a).A similar mixture of products was obtained throuch photolysis of the N-chloroamide (13).The reactions of the valine derivatives (5a) and (13) involve regioselective intermolecular transfer of the β-valinyl hydrogen.There is no evidence for reaction at the α-position.The β-chloroalanine derivative (23) was produced through reaction of N-benzoylalanine methyl ester (17a) with sulphuryl chloride and by photolysis of the N-chloroamide (22).Chlorination of the azetidinone (16a) gave (16b) in modest yield.These reactions establish the chemical validity of a regiospecific hydrogen-atom abstraction proposed in penicillin biosynthesis.

Regioselective Chlorination of N-Benzoylvaline Methyl Ester

Regioselective chlorination of valine derivatives establishes the chemical validity of a regiospecific hydrogen-atom abstraction proposed in penicillin biosynthesis and provides a viable synthetic method for direct and selective functionalisation of these compounds.