KR850004091A - Method for acylating cyclohex-2-en-1-one derivatives - Google Patents

Abstract

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Description

Method for acylating cyclohex-2-en-1-one derivatives

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Claims (12)

In the process for the preparation of the compound of general formula (I), the compound of general formula (II) is converted to the acid anhydride of general formula (III) in the presence of at least 3 molar equivalents of anhydrous aluminum chloride based on the compound of general formula (II). And reacting with an acid halide of formula (IV) or a mixture thereof. In this expression: The group is an aryl group or heteroaryl group optionally substituted with one or more electron giving groups; R ¹ is selected from alkyl, fluoroalkyl, alkenyl, alkynyl and phenyl; and R ² is selected from hydrogen, halogen, alkyl, cyano and alkoxycarbonyl; And R ³ is selected from alkyl, alkenyl, alkynyl, phenyl, substituted alkyl, substituted alkenyl, substituted alkynyl and substituted phenyl. The process according to claim 1, wherein the reaction is carried out in the presence of an aprotic organic solvent at a temperature of -20 ° C to 100 ° C. The compound according to claim 1 or 2, wherein in general formula (I) The group is a phenyl group of the general formula (V), a benzocycloalkyl group of the general formula (VI), an indenyl group of the general formula (VII) and a benzoheterocyclo clofentenyl group, a benzoazinyl group of the general formula (VII), A naphthyl group and a cycloalkyl, cycloalkenyl- and benzo-substituted azinyl group, and a furyl group and thienyl group of the general formula (III). In this formula: X can be the same or different and halogen; C ₁ -C ₆ alkyl; Halogen, hydroxy, C ₁ -C ₆ alkoxy and C ₁ -C ₆ a C ₁ -C ₆ alkyl substituted with a substituent selected from alkylthio; C ₂ -C ₆ alkenyl; C ₂ -C ₆ alkynyl hydroxy; C ₁ -C ₆ alkoxy; C ₁ -C ₆ alkoxy substituted with a substituent selected from halogen and C ₁ -C ₆ alkoxy; C ₁ -C ₆ alkenyloxy; C ₂ -C ₆ alkynyloxy; C ₁ -C ₆ alkylthio and R ⁴ and R ⁵ are independently selected from NR ⁴ R ⁵ groups independently selected from hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkanoyl, benzoyl and benzyl; 1 is an integer selected from 0 or 1-4; Wherein: W can be the same or different and is selected from C ₁ -C ₆ alkenyl and C ₂ -C ₆ alkynyl; X is as defined above; m is an integer selected from 0 or 1-4: n is an integer selected from 0 or 1-3; And p is an integer selected from 0 or 1,2. Wherein: A is selected from CH and N; B is selected from oxygen, sulfur, CH ₂ and NV, where V is hydrogen, C ₁ -C ₆ alkyl C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₇ cycloalkyl, benzyl And benzene ring is selected from benzyl substituted with one to three substituents selected from halogen, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₁ -C ₆ haloalkyl; X and m are as defined above; And q is an integer selected from 0 or 1-3; Wherein D, E, G and J are independently selected from CH, N and NZ, where Z is selected from oxygen and -YAn, Y is selected from C ₁ -C ₆ alkyl and benzyl and An is a halide, An anion selected from tetrafluoroborate, methosulfate and fluoro sulfate, provided that at least three of D, E, G and J are selected from N and NZ and at least one of D, E, G and J is selected from NZ; X and q are as defined above; Wherein D, E, G and J are independently selected from CH, N and NZ, where Z is selected from oxygen and -YAn, Y is selected from C ₁ -C ₆ alkyl and benzyl and An is a halide, An anion selected from tetrafluoroborate, methosulfate and fluoro sulfate, provided that at least one to at least three of D, E, G and J are selected from N and NZ and at least one of D, E, G and J to NZ Selected; Q is a saturated or unsaturated hydrocarbon chain having 2-5 carbon atoms; And X, m and q are as defined above; In which L is selected from oxygen and sulfur; X and q are as defined above; And R ¹ is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ fluoroalkyl, C ₂ -C ₆ alkenyl C ₂ -C ₆ alkynyl and phenyl; R ² is selected from hydrogen, halogen, cyano C ₁ -C ₆ alkyl and (C ₁ -C ₆ alkoxy) carbonyl; R ³ is C ₁ -C ₆ alkyl; C ₁ -C ₆ : alkoxy C ₁ -C ₆ alkylthio; C ₂ -C ₆ alkenyl; C ₂ -C ₆ alkynyl; Phenyl; And halogen, hydroxy, nitro, cyano, phenyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, (CC ₁ -C ₆ alkoxy) carbonyl, amino, N- C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ substituted with at least one substituent selected from (C ₁ -C ₆ alkyl) -amino and N, N- (C ₁ -C ₆ alkyl) amino -C ₆ alkynyl and phenyl. A compound according to claim 3, wherein in formulas (V), (VI), (iii), (iii), (iii) and (iii): X is C ₁ -C ₆ alkyl, halogen, C ₁ -C ₆ alkoxy And C ₁ -C ₆ alkylthio; W is methyl; A is CH; B is selected from oxygen, sulfur and N- (C ₁ -C ₆ alkyl); D, E, G and J are selected from CH and N; Q is selected from-(CH ₂ ) ₄ -and-(CH = CH) _2- ; L is selected from oxygen and sulfur; 1 is an integer selected from 2-4; m is an integer selected from 0 or 1,2; n and p are independently selected from 1 and 2; q is an integer selected from 1-3; R ¹ is selected from methyl, ethyl and n-propyl; R ² is hydrogen; And R ³ is selected from C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl and phenyl. A process for preparing a compound of formula (XII), wherein the compound of formula (XI) is prepared in the presence of at least 3 molar equivalents of anhydrous aluminium chloride based on the compound of formula (XI) A process for preparing a compound of formula (XII) characterized by reacting with anhydrides, acid halides of formula (IV) or mixtures thereof. Wherein: X is selected from C ₁ -C ₆ alkyl, halogen, C ₁ -C ₆ alkoxy and C ₁ -C ₆ alkylthio; R ¹ is selected from methyl, ethyl and n-propyl; R ² is hydrogen; R ³ is C ₁ -C ₆ alkyl; C ₂ -C ₆ alkenyl; Phenyl C ₁ -C ₆ alkoxy; C ₁ -C ₆ alkylthio; Halogen, (C ₁ -C ₆ alkoxy) carbonyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ a C ₁ -C ₆ alkyl substituted with one or more substituents selected from alkylthio and phenyl; And phenyl substituted with one or more substituents selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy; And 1 is selected from an integer of 2-4; The compound of claim 5, wherein the compound is of formula (XII); X is selected from halogen, methyl and methoxy; R ¹ is selected from ethyl and n-propyl; R ² is hydrogen; R ³ is selected from methyl, ethyl, chloromethyl, bromomethyl, ethoxycarbonylmethyl, methylthiomethyl, benzyl, allyl, ethylthio, phenyl, methoxyphenyl, nitrophenyl and cyanophenyl; 1 is selected from an integer of 2-4. The compound of formula (XII) according to claim 5 or 6; X is methyl; R ¹ is selected from ethyl and n-propyl; R ² is hydrogen; R ³ is methyl; And 1 is selected from integers of 3 and 4. In the process for preparing a compound of formula (XIV), the compound of formula (XIII) is prepared in the presence of at least 3 molar equivalents of anhydrous aluminium chloride based on the compound of formula (XIII). A process for preparing a compound of formula (XIV) characterized by reacting with an acid anhydride, an acid halide of formula (IV) or a mixture thereof. In this formula; X is selected from C ₁ -C ₆ alkyl, halogen, C ₁ -C ₆ alkoxy and C ₁ -C ₆ alkylthio; R ¹ is selected from methyl, ethyl and n-propyl; R ² is hydrogen; R ³ is C ₁ -C ₆ alkyl; C ₂ -C ₆ alkenyl; Phenyl C ₁ -C ₆ alkoxy; C ₁ -C ₆ alkylthio; Halogen, (C ₁ -C ₆ alkoxy) carbonyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ a C ₁ -C ₆ alkyl substituted with one or more substituents selected from alkylthio and phenyl; And phenyl substituted with one or more substituents selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy; m is selected from integers of 0 and 1,2; And q is selected from an integer of 1-3. The compound of claim 8, wherein: in the compound of formula (XIV): X is selected from halogen, methyl and methoxy; R ¹ is selected from ethyl and n-propyl; R ² is hydrogen; R ³ is selected from methyl, ethyl, chloromethyl, bromomethyl, ethoxycarbonylmethyl, methylthiomethyl, benzyl, allyl, ethylthio, phenyl, methoxyphenyl, nitrophenyl and cyanophenyl; m is selected from integers of 0 and 1,2; And q is selected from integers of 1-3. The compound according to claim 8 or 9, wherein in the compound of compound (XIII): X methyl; R ¹ is selected from ethyl and n-propyl; R ² is hydrogen; R ³ is methyl; m is selected from integers of 0 and 1,2; And q is selected from integers of 1-3. The process according to any one of claims 5 to 10, wherein the reaction is carried out in the presence of an aprotic organic solvent at a temperature of -20 ° C to 100 ° C. The manufacturing method according to any one of claims 1 to 11, wherein the manufacturing method is substantially carried out by the method according to any one of Examples 1 to 3 described above. ※ Note: The disclosure is based on the initial application.