Synthesis of cyclic compounds
AssigneeUnisearch Limited
InventorsNaresh Kumar, Roger Wayne Read
Life of this patent
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Abstract
A method for the preparation of a compound of formula (II) wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic; R3, R4, R5 and R6 are independently or all hydrogen or halogen; provided that at least two of the R3, R4, R5 and R6 are halogens.
Claims56
A method for the preparation of a compound of formula II
- 22
- wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen;
- the method comprising cyclising a compound of formula I
- 23
- wherein R1, R2, R3, R4, R5 and R6 are as defined above, wherein the cyclisation is carried out in the presence of a mild acid catalyst or a dehydrating agent or a mixture thereof, optionally in the presence of solvent.
A method according to any one of the preceding claims wherein at least one of R5 and R6 is Br.
A method according to any one of the preceding claims, wherein the reaction is carried out in the presence of a mild acid catalyst(s).
A method according to any one of the preceding claims which is carried out in the presence of a dehydrating agent.
A method according to any one of the preceding claims wherein the cyclisation is carried out in the presence of at least one solvent.
A method according to any one of the preceding claims wherein the cyclisation reaction is performed at a temperature in the range of from about 20-150° C.
A method according to any one of the preceding claims, wherein the cyclisation reaction is carried out for at least 2 hours.
A compound of formula II produced by a method in accordance with any one of the preceding claims.
A compound of formula I
- 24
- wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen;
- and provided that at least two of the R3, R4, R5 and R6 are halogens;
A tetrahydro-2(5H)-furanone derivative of formula II,
- 26
- wherein R1, and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen;
- and provided that at least two of the R3, R4, R5 and R6 are halogens;
- excluding compounds in which:
- R1=R2=H, R3=R4=Cl and R5=R6=Br;
- and
- R1, =R2=R5=R6=H and R3=R4=Cl.
A method for the dehydrohalogenation of a compound of formula II
- 28
- wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen,
- provided that at least two of the R3, R4, R5 and R6 are halogens;
- to prepare a compound of formula IIIa or IIIb;
- 29
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen
- R1 and R3 are independently or both hydrogen or halogen;
- 30
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R3 and R4 are hydrogen and R1 is a halogen;
- the method comprising contacting a compound of formula II with a base.
A compound according to formula IIIa or IIIb.
- 33
- wherein in figure IIIa R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- excluding compounds in which:
- R1=H, R2=Me or Ph, R3=I, R4=H;
- and
- R1=H, R2=OMe, R3=Cl, R4=Cl;
- 34
- wherein in formula IIIb R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R3 and R4 are hydrogen;
- and
- R1 is a halogen,
A method for the halogenation of a compound of formula II, IIIa or IIIb
- 35
- wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen;
- and provided that least two of the R3, R4, R5 and R6 are halogens;
- 36
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen
- R1 and R3 are independently or both hydrogen or halogen;
- 37
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R3 and R4 are hydrogen and R1 is a halogen;
- to prepare a compound of formula IV
- 38
- wherein R2 is independently H, halogen, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophilic or fluorophilic;
- R4 is selected from halogen, OH and alkoxy;
- R5 are halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- and “” is a single bond or double bond,
- the method comprising contacting a compound of formula II, IIIa, or IIIb with a halogenating agent optionally in the presence of at least one unreactive or reactive solvent or reagent.
A compound of formula IV,
- 41
- wherein R2 is independently alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophilic or fluorophilic;
- R4 is selected from halogen, OH and Oalkyl;
- R5 are halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- and
- “” is a single bond or double bond.
A method for the debydrohalogenation of a compound of formula IV:
- 42
- wherein R2 is independently H, halogen, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophilic or fluorophilic;
- R4 is selected from halogen, OH and Oalkyl;
- R5 are halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- and “” is a single bond or double bond.
- to prepare a compound of formula V
- 43
- wherein R2 is a H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- the method comprising contacting a compound of formula IV with a base.
A method of tandem cyclisation, dehalogenation, rehalogenaton and dehydrohalogenation of compounds of formula:
- 47
- wherein R1 and R2 are independently H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl, or arylalkyl whether unsubstituted or substituted, optionally interrupted by one or more hetero atoms, straight chain or branched chain, hydrophilic, hydrophobic or fluorophilic;
- R3, R4, R5 and R6 are independently or all hydrogen or halogen;
- and provided that at least two of the R3, R4, R5 and R6 are halogens;
- to form a compound of formula (Vl), the method comprising contacting the compound with a strong acid
- 48
- wherein R2 is a H, halogen, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 is hydrogen;
- and
- R3 is a hydrogen or halogen.
A compound of formula VI:
- 50
- wherein R2 is an alkyl, alkoxy, oxoalyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 is a hydrogen;
- and
- R3 is a hydrogen or halogen;
- excluding a compounds in which R1=H, R2Me or Ph, R3=I, R4=H;
- and
- R1=H, R2=OMe, R3=Cl, R4=Cl.
A compound of formula (VII):
- 51
- wherein R2 is a H, alkyl, alkoxy, polyethyleneglycyl oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a hydrogen, halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- Z is independently selected from the group R2, halogen, OC(O)R2, ═O, amine azide, thiol R2, mercaptoaryl, arylalkoxy, mercaptoarylalkyl, SC(O)R2, OS(O)2R2, NHC(O)R2, ═NR2 or NHR2,
- prepared by functionalizing a fimbrolide of formula (VIII) wherein, R1, R2, R3 and R4 are as defined above, with reagents selected from the group consisting of halogenating, oxidising agents, nucleophiles and electrophiles.
- 52
An oligomer or polymer formed by oligomerising or polymerising a compound selected from the group consisting of compounds of formula IIIa, IIIb-VII, directly or with one or more monomers
- 53
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen
- R1 and R3 are independently or both hydrogen or halogen;
- 54
- wherein R2 is an alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R3 and R4 are hydrogen;
- and
- R1 is a halogen.
- 55
- wherein R2 is independently H, halogen, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophilic or fluorophilic;
- R4 is selected from halogen, OH and Oalkyl;
- R5 are halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- and “” is a single bond or double bond.
- 56
- wherein R2 is a H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- 57
- wherein R2 is a H, halogen, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a halogen;
- R1 is hydrogen;
- and
- R3 is a hydrogen or halogen;
- 58
- wherein R2 is a H, alkyl, alkoxy, oxoalkyl, alkenyl, aryl or arylalkyl whether unsubstituted or substituted, straight chain or branched chain, hydrophobic, hydrophilic or fluorophilic;
- R4 is a hydrogen, halogen;
- R1 and R3 are independently or both hydrogen or halogen;
- Z is independently selected from the group R2, halogen, OC(O)R2, ═O, amine azide, thiol, R2, mercaptoaryl, arylalkoxy, mercaptoarylalkyl, SC(O)R2, OS(O)2R2, NHC(O)R2, ═NR2 or NHR2,
An article incorporating at least one compound of formula II to VII in a surface coating(s) or polymer(s) through the newly introduced functionality on the alkyl chain or the alkyl chain itself via direct polymerisation or copolymerisation with suitable monomers.
Dependencies are inferred from the claim text.