公开(公告)号：JPH10147548A

公开(公告)日：1998-06-02

申请号：JP31011997

申请日：1997-11-12

Applicant: BASF AG

Inventor： ETZRODT HEINZ DR ,  STROEZEL MANFRED ,  WELLER DIETMAR DR ,  JAEDICKE HAGEN DR

IPC: C07C45/69 ,  C07C45/67 ,  C07C45/71 ,  C07C45/76 ,  C07C49/203

Abstract: PROBLEM TO BE SOLVED: To obtain the subject compound useful as an intermediate product for the production of perfumes, vitamin A, etc., by Carrol reaction in a specific solvent. SOLUTION: This γ,δ-unsaturated ketone, e.g. 2-methyl-2-hepten-6-one is obtained by using a cyclic carbonate of formula I (R -R are each H, methyl, etc.; R is H, isopropyl, etc.), e.g. ethylene carbonate, etc., a γ-lactone of formula II, e.g. γ-butyrolactone, etc., as a solvent, and reacting vinycarbinol or propargyl alcohol with an acetoacetic alkyl ester or diketene, then in the presence of an aluminum catalyst and at 120-220 deg.C, by thermal rearrangement reaction of the resultant acetoacetate to the aimed γ,δ-unsaturated ketone.

公开(公告)号：DK0983988T3

公开(公告)日：2002-03-25

申请号：DK99117101

申请日：1999-08-31

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  WELLER DIETMAR DR ,  BOCKSTIEGEL BERNHARD DR ,  REIMER KLAUS ,  KAIBEL GERD DR ,  JAEDICKE HAGEN DR

IPC: B01J31/14 ,  B01D3/00 ,  B01D3/14 ,  B01D3/32 ,  B01J10/00 ,  B01J19/24 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C45/82 ,  C07C49/203 ,  C07C67/54 ,  C07C69/72

Abstract: Continuous production of 5-alken-2-one or 3,5-alkadien-2-one derivatives (I) by reacting a 1-alken-3-ol or 1-alkyn-3-ol derivative (II) with an alkyl acetoacetate (III) in a fractionation column to form an acetoacetate and alcohol involves (i) removing the alcohol and (ii) contacting the acetoacetate with catalyst in the lower part or bottom of the column to form (I). Continuous production of unsaturated ketones of formula (I) by reacting an unsaturated alcohol of formula (II) with an alkyl acetoacetate of formula (III) in the presence of an organoaluminum catalyst is carried out by: (a) reacting (II) with (III) on the plates of a fractionation column to form the acetoacetate of (II) and an alcohol of formula R OH; (b) removing the alcohol in the overhead stream from the column; (c) contacting the acetoacetate of (II) with the catalyst in the lower part or bottom of the column to form (I) and CO2; (d) removing the CO2 in the overhead stream from the column; and (e) withdrawing (I) in the bottoms stream from the column. R = 1-4C alkyl; R = 1-37C (un)saturated aliphatic hydrocarbyl (optionally substituted by methoxy groups), 4-12C cycloalkyl or 5-30C cycloalkylalkyl; and R = 1-5C alkyl.

公开(公告)号：DE19647117A1

公开(公告)日：1998-05-28

申请号：DE19647117

申请日：1996-11-14

Applicant: BASF AG

Inventor： ETZRODT HEINZ DR ,  STROEZEL MANFRED ,  WELLER DIETMAR DR ,  JAEDICKE HAGEN DR

IPC: C07C45/69 ,  C07C45/67 ,  C07C45/71 ,  C07C45/76 ,  C07C49/203 ,  C07C45/56

公开(公告)号：SI0909750T1

公开(公告)日：2002-12-31

申请号：SI9830255

申请日：1998-10-12

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  BOCKSTIEGEL BERNHARD DR ,  JAEDICKE HAGEN DR ,  WELLER DIETMAR DR ,  LAUPICHLER LOTHAR DR ,  REIMER KLAUS

IPC: B01J31/22 ,  C07C45/67 ,  C07C49/203 ,  C07F5/06

公开(公告)号：ES2172277T3

公开(公告)日：2002-09-16

申请号：ES99117101

申请日：1999-08-31

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  WELLER DIETMAR DR ,  BOCKSTIEGEL BERNHARD DR ,  REIMER KLAUS

IPC: B01J31/14 ,  B01D3/00 ,  B01D3/14 ,  B01D3/32 ,  B01J10/00 ,  B01J19/24 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C45/82 ,  C07C49/203 ,  C07C67/54 ,  C07C69/72

Abstract: Continuous production of 5-alken-2-one or 3,5-alkadien-2-one derivatives (I) by reacting a 1-alken-3-ol or 1-alkyn-3-ol derivative (II) with an alkyl acetoacetate (III) in a fractionation column to form an acetoacetate and alcohol involves (i) removing the alcohol and (ii) contacting the acetoacetate with catalyst in the lower part or bottom of the column to form (I). Continuous production of unsaturated ketones of formula (I) by reacting an unsaturated alcohol of formula (II) with an alkyl acetoacetate of formula (III) in the presence of an organoaluminum catalyst is carried out by: (a) reacting (II) with (III) on the plates of a fractionation column to form the acetoacetate of (II) and an alcohol of formula R OH; (b) removing the alcohol in the overhead stream from the column; (c) contacting the acetoacetate of (II) with the catalyst in the lower part or bottom of the column to form (I) and CO2; (d) removing the CO2 in the overhead stream from the column; and (e) withdrawing (I) in the bottoms stream from the column. R = 1-4C alkyl; R = 1-37C (un)saturated aliphatic hydrocarbyl (optionally substituted by methoxy groups), 4-12C cycloalkyl or 5-30C cycloalkylalkyl; and R = 1-5C alkyl.

公开(公告)号：ES2184187T3

公开(公告)日：2003-04-01

申请号：ES98119215

申请日：1998-10-12

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  BOCKSTIEGEL BERNHARD DR ,  JAEDICKE HAGEN DR ,  WELLER DIETMAR DR

IPC: B01J31/02 ,  B01J31/14 ,  B01J31/22 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C49/203 ,  C07F5/06

Abstract: Preparation of gamma , delta -unsaturated ketones (I) by modified Carroll reaction is catalysed by a stable liquid aluminum acetoacetate compound or mixture of such compounds. Some such catalyst mixtures are new. Preparation of gamma , delta -unsaturated ketones of formula (I) involves modified Carroll reaction of an allyl alcohol of formula (II) with diketene or an alkyl acetoacetate of formula (III) in presence of an aluminum catalyst. R1 = H or 1-20C, saturated or unsaturated, branched hydrocarbyl; R2 = 1-5C alkyl. The novelty is that the catalyst consists of an aluminum compound (or aluminum compound mixture) which is a stable liquid at room temperature and contains at least one alkyl acetoacetate-forming group and 1 or 2 alkoxy groups or exclusively alkyl acetoacetate forming groups which are esterified sec. butanol or isobutanol or with at least two different alkanols. Independent claims are included for: (1) new mixtures of aluminum tris-acetoacetates of formula (V) which are liquid at room temperature; and (2) the preparation of mixtures as in (1). R3 = 1-5C alkyl, preferably Me or Et; R4 = 3-10C alkyl, preferably CHMe2, CH(Me)Et, CMe3 or CH(Me)-C3H7; R5 = 1-10C alkyl, preferably Me, Et, CHMe2, CH(Me)Et or CH(Me)-C3H7; provided that R3-R5 are not all the same. A further Independent claim relates to the continuous preparation of compounds (V) (or their mixtures), having the narrower proviso that R3-R5 can only be the same if they are -CH(Me)Et or -CH2CHMe2, which are liquid at room temperature. The process involves continuously reacting 1 mole of aluminum alcoholate of formula (VI) with 3-10 moles of (III), or with at least 3 moles of a mixture of 2 or 3 different compounds (III), optionally dissolved in an inert solvent. Reaction is at 100-250 (preferably 150-200) degrees C and 1-100 (preferably 1-10) bars with a dwell time of 5-120 (preferably 15-45) minutes, the pressure and temperature being such that no gas phase is formed in the reaction vessel. R6 = 2-10C alkyl, preferably -CH2CHMe2, -CH(Me)Et or -CH(Me)C3H7; provided that R2 and R6 can only be the same if they are -CH(Me)Et or -CH2CHMe2.

公开(公告)号：DE59805594D1

公开(公告)日：2002-10-24

申请号：DE59805594

申请日：1998-10-12

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  BOCKSTIEGEL BERNHARD DR ,  JAEDICKE HAGEN DR ,  WELLER DIETMAR DR ,  LAUPICHLER LOTHAR DR ,  REIMER KLAUS

IPC: B01J31/02 ,  B01J31/14 ,  B01J31/22 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C49/203 ,  C07F5/06

Abstract: Preparation of gamma , delta -unsaturated ketones (I) by modified Carroll reaction is catalysed by a stable liquid aluminum acetoacetate compound or mixture of such compounds. Some such catalyst mixtures are new. Preparation of gamma , delta -unsaturated ketones of formula (I) involves modified Carroll reaction of an allyl alcohol of formula (II) with diketene or an alkyl acetoacetate of formula (III) in presence of an aluminum catalyst. R1 = H or 1-20C, saturated or unsaturated, branched hydrocarbyl; R2 = 1-5C alkyl. The novelty is that the catalyst consists of an aluminum compound (or aluminum compound mixture) which is a stable liquid at room temperature and contains at least one alkyl acetoacetate-forming group and 1 or 2 alkoxy groups or exclusively alkyl acetoacetate forming groups which are esterified sec. butanol or isobutanol or with at least two different alkanols. Independent claims are included for: (1) new mixtures of aluminum tris-acetoacetates of formula (V) which are liquid at room temperature; and (2) the preparation of mixtures as in (1). R3 = 1-5C alkyl, preferably Me or Et; R4 = 3-10C alkyl, preferably CHMe2, CH(Me)Et, CMe3 or CH(Me)-C3H7; R5 = 1-10C alkyl, preferably Me, Et, CHMe2, CH(Me)Et or CH(Me)-C3H7; provided that R3-R5 are not all the same. A further Independent claim relates to the continuous preparation of compounds (V) (or their mixtures), having the narrower proviso that R3-R5 can only be the same if they are -CH(Me)Et or -CH2CHMe2, which are liquid at room temperature. The process involves continuously reacting 1 mole of aluminum alcoholate of formula (VI) with 3-10 moles of (III), or with at least 3 moles of a mixture of 2 or 3 different compounds (III), optionally dissolved in an inert solvent. Reaction is at 100-250 (preferably 150-200) degrees C and 1-100 (preferably 1-10) bars with a dwell time of 5-120 (preferably 15-45) minutes, the pressure and temperature being such that no gas phase is formed in the reaction vessel. R6 = 2-10C alkyl, preferably -CH2CHMe2, -CH(Me)Et or -CH(Me)C3H7; provided that R2 and R6 can only be the same if they are -CH(Me)Et or -CH2CHMe2.

公开(公告)号：DK0909750T3

公开(公告)日：2002-10-14

申请号：DK98119215

申请日：1998-10-12

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  BOCKSTIEGEL BERNHARD DR ,  JAEDICKE HAGEN DR ,  WELLER DIETMAR DR ,  LAUPICHLER LOTHAR DR ,  REIMER KLAUS

IPC: B01J31/02 ,  B01J31/14 ,  B01J31/22 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C49/203 ,  C07F5/06

Abstract: Preparation of gamma , delta -unsaturated ketones (I) by modified Carroll reaction is catalysed by a stable liquid aluminum acetoacetate compound or mixture of such compounds. Some such catalyst mixtures are new. Preparation of gamma , delta -unsaturated ketones of formula (I) involves modified Carroll reaction of an allyl alcohol of formula (II) with diketene or an alkyl acetoacetate of formula (III) in presence of an aluminum catalyst. R1 = H or 1-20C, saturated or unsaturated, branched hydrocarbyl; R2 = 1-5C alkyl. The novelty is that the catalyst consists of an aluminum compound (or aluminum compound mixture) which is a stable liquid at room temperature and contains at least one alkyl acetoacetate-forming group and 1 or 2 alkoxy groups or exclusively alkyl acetoacetate forming groups which are esterified sec. butanol or isobutanol or with at least two different alkanols. Independent claims are included for: (1) new mixtures of aluminum tris-acetoacetates of formula (V) which are liquid at room temperature; and (2) the preparation of mixtures as in (1). R3 = 1-5C alkyl, preferably Me or Et; R4 = 3-10C alkyl, preferably CHMe2, CH(Me)Et, CMe3 or CH(Me)-C3H7; R5 = 1-10C alkyl, preferably Me, Et, CHMe2, CH(Me)Et or CH(Me)-C3H7; provided that R3-R5 are not all the same. A further Independent claim relates to the continuous preparation of compounds (V) (or their mixtures), having the narrower proviso that R3-R5 can only be the same if they are -CH(Me)Et or -CH2CHMe2, which are liquid at room temperature. The process involves continuously reacting 1 mole of aluminum alcoholate of formula (VI) with 3-10 moles of (III), or with at least 3 moles of a mixture of 2 or 3 different compounds (III), optionally dissolved in an inert solvent. Reaction is at 100-250 (preferably 150-200) degrees C and 1-100 (preferably 1-10) bars with a dwell time of 5-120 (preferably 15-45) minutes, the pressure and temperature being such that no gas phase is formed in the reaction vessel. R6 = 2-10C alkyl, preferably -CH2CHMe2, -CH(Me)Et or -CH(Me)C3H7; provided that R2 and R6 can only be the same if they are -CH(Me)Et or -CH2CHMe2.

公开(公告)号：DE19619557C1

公开(公告)日：1997-11-20

申请号：DE19619557

申请日：1996-05-14

Applicant: BASF AG

Inventor： RHEUDE UDO DR ,  HOERCHER ULRICH DR ,  WELLER DIETMAR DR ,  STROEZEL MANFRED

IPC: C07B37/10 ,  C07C20060101 ,  C07C49/21 ,  C07C403/14 ,  C07C403/16

Abstract: A process for the continuous production of alpha and/or beta -ionones or homologous compounds by means of concentrated sulphuric acid at temperatures of 20 to 90 DEG C in the presence of organic solvents or diluents with cooling, and the subsequent halting of the reaction by the hydrolysis of the reaction mixtures with water or dilute sulphuric acid, in which the cyclization of the pseudo-ionones and the subsequent hydrolysis of the reaction mixture is performed in a practically adiabatic reaction in one or more successive reaction mixing pump(s) consisting of a rotational symetrical mixing chamber formed by a peripheral wall and two faces and driven mixing rotor of a material unaffected by sulphuric acid, where the mixing chamber has at least one inlet for each component and an outlet for the reaction mixture and annular chanels in fluid communication with each other in the faces, and the heat of reaction of both reactions is partly or fully evacuated with the aid of a downstream heat exchanger.

公开(公告)号：ES2198106T3

公开(公告)日：2004-01-16

申请号：ES99122634

申请日：1999-11-13

Applicant: BASF AG

Inventor： OOST CARSTEN DR ,  STROEZEL MANFRED ,  ETZRODT HEINZ DR ,  WELLER DIETMAR DR ,  KAIBEL GERD DR ,  JAEDICKE HAGEN DR

IPC: B01J31/12 ,  B01J19/18 ,  C07B61/00 ,  C07C45/67 ,  C07C45/68 ,  C07C45/70 ,  C07C49/203

Abstract: Preparation of unsaturated methyl ketones(I), from an unsaturated alcohol(II) and alkyl acetoacetate(III) in the presence of an organo-aluminum catalyst(IV) comprises: (a) supplying (II) and (IV) to a reactor with a distillation column, (b) making temperature to be 170-250 degrees C under elevated pressure, (c) dosing the mixture with (III) and (d) maintaining a constant (III) content of 0.1-10 wt.% during the reaction. Preparation of unsaturated ketones of formula (I) involves reaction of an unsaturated alcohol of formula (II) with an alkyl acetoacetate of formula (III), in presence of 0.1-5 mol. % (based on (II)) of an organo-aluminum compound catalyst (IV), with elimination and distillative separation of the alcohol R3OH formed in the reaction, in a reactor system provided with a distillation column. Reaction is carried out by: (a) supplying (I (which boils at less than 140 degrees C), without a solvent, and (IV) to the reaction vessel, (b) adjusting the temperature to a value as constant as possible in the range 170-250 degrees C under elevated pressure, (c) dosing the mixture with (III) and (d) maintaining a (III) content as constant as possible in the range 0.1-10 wt. % during the reaction. Dotted line = optional bond; R1 = Me or Et; R2, R3 = 1-4C alkyl.