EP0244143A2
Expired / Lapsed
EP
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Substituted dioxanones and dioxinones
Assignee: Imperial Chemical Industries Ltd
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Filing: 1987-04-21
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Granted: —
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Expires: 2007-04-21
Abstract
Abstract Compounds of the formulae: wherein R¹, R², R³ and R⁴ have a wide range of values are described as useful intermediates in the preparation of pharmaceuticals, etc, in particular in the preparation of optically active β-hydroxy α-substituted carboxylic acids. Processes for their preparation are described.
Inventors
- 👤 Dieter Seebach
- 👤 Jurg Zimmermann
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-31 22:25
CPC Classifications
C; C07; C07D; C07D319/00; C07D319/04; C07D319/06
Claims Analysis
Total Claims: 8
Claim 1
Independent Claim
443 words
A process for preparing a compound of the formula (VI): wherein: R¹ is an organic group (bonded via a carbon atom), R² is hydrogen or an organic group (bonded via a carbon atom), R³ is hydrogen, amino, protected amino, hydroxy, protected hydroxy or an organic group (bonded via a carbon atom), and R⁴ is hydrogen, an organic group (bonded via a carbon atom) or is the residue of a heteroelectrophile: with the proviso that CR³R⁴ is not CH₂, CHCH₃ or C(CH₃)₂: which process comprises (a) reacting a compound of the formula (VII) and a compound of the formula (VIII): R¹CHO (VII) R²CH(OH)CHR³¹COOH (VIII) wherein R¹ and R² are as defined hereinbefore and R³¹ is hydrogen, amino, protected amino, hydroxy or protected hydroxy, to form a compound of the formula (VI) wherein R³ is a group R³¹ as hereinabove defined and R⁴ is hydrogen, and thereafter, if necessary: (i) when R³ and R⁴ are both hydrogen, forming an enolate of the formula (IX): wherein R¹ and R² are as hereinbefore defined, and M¹ is a counter-ion or protecting group, and subsequently reacting said enolate with an electrophilic source of the group R⁴ wherein R⁴ is an organic group to form a compound of the formula (VI) wherein R¹ and R² are as hereinbefore defined, one of R³ and R⁴ is an organic group and the other is hydrogen; or (ii) when R³ is a group R³¹ as hereinbefore defined and R⁴ is hydrogen, forming an enolate of the formula (X): wherein R¹, R², R³¹ and M¹ are as hereinbefore defined, and subsequently reacting said enolate with a heteroelectrophile to form a compound of the formula (VI) wherein R¹ and R² are as hereinbefore defined, R³ is a group R³¹ and R⁴ is the residue of a heteroelectrophile; and furthermore, is necessary: (iii) when R⁴ is hydrogen and R³ is an organic group in the compound of the formula (VI), reacting said compound to form an enolate of the formula (XI): wherein R¹ and R³ are independently organic groups, R² is hydrogen or an organic group and M² is a counter-ion or protecting group, and subsequently either: reacting said enolate with an electrophilic source of the group R⁴ wherein R⁴ is an organic group to form a compound of the formula (VI) wherein R¹, R³ and R⁴ are independently organic groups and R² is hydrogen or an organic group; or reacting said enolate with a heteroelectrophile to form a compound of the formula (VI) wherein R¹ and R³ are independently organic groups, R² is hydrogen or an organic group and R⁴ is the residue of a heteroelectrophile; and subsequently, if desired, removing any protecting groups.
Claim 2
Dependent Claim
443 words
A process for preparing a compound of the formula (VI): wherein: R¹ is an organic group (bonded via a carbon atom), R² is hydrogen or an organic group (bonded via a carbon atom), R³ is hydrogen, amino, protected amino, hydroxy, protected hydroxy or an organic group (bonded via a carbon atom), and R⁴ is hydrogen, an organic group (bonded via a carbon atom) or is the residue of a heteroelectrophile: with the proviso that CR³R⁴ is not CH₂, CHCH₃ or C(CH₃)₂: which process comprises (a) reacting a compound of the formula (VII) and a compound of the formula (VIII): R¹CHO (VII) R²CH(OH)CHR³¹COOH (VIII) wherein R¹ and R² are as defined hereinbefore and R³¹ is hydrogen, amino, protected amino, hydroxy or protected hydroxy, to form a compound of the formula (VI) wherein R³ is a group R³¹ as hereinabove defined and R⁴ is hydrogen, and thereafter, if necessary: (i) when R³ and R⁴ are both hydrogen, forming an enolate of the formula (IX): wherein R¹ and R² are as hereinbefore defined, and M¹ is a counter-ion or protecting group, and subsequently reacting said enolate with an electrophilic source of the group R⁴ wherein R⁴ is an organic group to form a compound of the formula (VI) wherein R¹ and R² are as hereinbefore defined, one of R³ and R⁴ is an organic group and the other is hydrogen; or (ii) when R³ is a group R³¹ as hereinbefore defined and R⁴ is hydrogen, forming an enolate of the formula (X): wherein R¹, R², R³¹ and M¹ are as hereinbefore defined, and subsequently reacting said enolate with a heteroelectrophile to form a compound of the formula (VI) wherein R¹ and R² are as hereinbefore defined, R³ is a group R³¹ and R⁴ is the residue of a heteroelectrophile; and furthermore, is necessary: (iii) when R⁴ is hydrogen and R³ is an organic group in the compound of the formula (VI), reacting said compound to form an enolate of the formula (XI): wherein R¹ and R³ are independently organic groups, R² is hydrogen or an organic group and M² is a counter-ion or protecting group, and subsequently either: reacting said enolate with an electrophilic source of the group R⁴ wherein R⁴ is an organic group to form a compound of the formula (VI) wherein R¹, R³ and R⁴ are independently organic groups and R² is hydrogen or an organic group; or reacting said enolate with a heteroelectrophile to form a compound of the formula (VI) wherein R¹ and R³ are independently organic groups, R² is hydrogen or an organic group and R⁴ is the residue of a heteroelectrophile; and subsequently, if desired, removing any protecting groups.
Claim 3
Dependent Claim
79 words
A process as depicted in claim 1 for preparing a compound of the formula (VI): in optically active form wherein: R¹ is an organic group (bonded via a carbon atom), R² is hydrogen or an organic group (bonded via a carbon atom), R³ is hydrogen, amino, protected amino, hydroxy, protected hydroxy or an organic group (bonded via a carbon atom), and R⁴ is hydrogen, an organic group (bonded via a carbon atom) or is the residue of a heteroelectrophile.
Claim 4
Dependent Claim
23 words
A process according to either claim 1 or claim 2 for preparing a compound wherein R² is hydrogen, methyl, ethyl, carboxy or trifluoromethyl.
Claim 5
Dependent Claim
19 words
A process according to any one of claims 1 to 3 for preparing a compound wherein R³ is hydrogen.
Claim 6
Dependent Claim
28 words
A process according to any one of claims 1 to 4 for preparing a compound wherein R⁴ is C 1-4 alkyl, C 2-4 alkenyl or phenylC 1-4 alkyl.
Claim 7
Dependent Claim
35 words
A process for preparing a compound of the formula (XVII): and derivatives thereof, wherein R²,R³ and R⁴ are as defined in claim 1, which comprises the acid hydrolysis of a compound of the formula (VI).
Claim 8
Dependent Claim
112 words
A process for preparing a compound of the formula (XVIII): wherein R¹, R² and R³ are as defined in claim 1 with the proviso that R³ is not hydrogen or methyl: which comprises (i) eliminating the elements R⁴¹ and hydrogen from a compound of the formula (XIX): wherein R¹, R² and R³ are as defined in claim 1 and R⁴¹ is a leaving group; or (ii) dehydrogenating a compound of the formula (VI), as defined in claim 1, wherein R⁴ is hydrogen; or (III) to form a compound of the formula (XVIII) wherein R³ is hydrogen, catalytically hydrogenating a compound of the formula (XX): wherein R¹ and R² are as hereinbefore defined.
References Cited (Backward Citations)
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