公开(公告)号：JPH11116552A

公开(公告)日：1999-04-27

申请号：JP15588798

申请日：1998-06-04

Applicant: BASF AG

Inventor： PAUST JOACHIM ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: PROBLEM TO BE SOLVED: To obtain a zeaxanthin in high yield from a readily available trimethylcyclohexanone through few reaction processes via an important intermediate. SOLUTION: This zeaxanthin is obtained through the following process: (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone of formula I is reacted with dichloromethyllithium, the reaction mixture is heated to form a bicyclic 10C- aldehyde of formula II, which is then reacted with acetone or the like to form a bicyclic 13C-ketone, which, in turn, is converted to a 15C-carbinol of formula III; the carbinol is then reacted with a triarylphosphine to form a mixture of a 15C triarylphosphonium salt of formula IV and an iso-isomer (Ar is an aryl; X is one equivalent anion of an strong acid), and in each case, about 2 mol of the above reaction mixture formed is subjected to double Wittig reaction with 2,7-dimethyl-2,4,6-octatrienedial of formula V to effect conversion to the objective (3R,3'R)-zeaxanthin of formula VI.

公开(公告)号：DE19723480A1

公开(公告)日：1998-12-10

申请号：DE19723480

申请日：1997-06-04

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：AT203518T

公开(公告)日：2001-08-15

申请号：AT98109285

申请日：1998-05-22

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：DE19543619A1

公开(公告)日：1997-05-28

申请号：DE19543619

申请日：1995-11-23

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG ,  HARTMANN HORST

IPC: C07C45/61 ,  C07C45/82 ,  C07C49/497 ,  C07B57/00 ,  C07C49/713

Abstract: Preparation of pure trans- and cis-4-hydroxy-2,2,6-trimethylcyclohexan-1-one of formulae (I) and (II) respectively comprises separation of a mixture of these isomers by fractional distillation in a column with 30-80 theoretical plates at 50-130 degrees C and 0.1-5 mbar.

公开(公告)号：PT882709E

公开(公告)日：2002-01-30

申请号：PT98109285

申请日：1998-05-22

Applicant: BASF AG

Inventor： PAUST JOACHIM ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：GR3036401T3

公开(公告)日：2001-11-30

申请号：GR20010401258

申请日：2001-08-16

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：ES2161000T3

公开(公告)日：2001-11-16

申请号：ES98109285

申请日：1998-05-22

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：DK0882709T3

公开(公告)日：2001-09-24

申请号：DK98109285

申请日：1998-05-22

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：DE59801069D1

公开(公告)日：2001-08-30

申请号：DE59801069

申请日：1998-05-22

Applicant: BASF AG

Inventor： PAUST DR ,  KRIEGL WOLFGANG

IPC: C07C403/24 ,  C07D493/08 ,  C07F9/50 ,  C07F9/54

Abstract: Preparation of (3R,3'R)-zeaxanthin (I) comprises: (i) reacting (4R)-4-hydroxy-2,2,6-trimethyl-cyclohexanone (II) with dichloromethyl lithium in an inert solvent at -120 to -40 degrees C and warming the reaction mixture to 20-60 degrees C; (ii) reacting the obtained (4R,6R)-1-formyl-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (IV) (in isolated form or directly in the reaction mixture) with acetone or a dialkyl (2-oxo-propyl)-phosphonate; (iii) converting the obtained (4R,6R)-1-(3-oxo-but-1-en-1-yl)-2,2,6-trimethyl-7-oxa-bicyclo (2.2.1) heptane of formula (V) into (4R,6R)-1-(3-hydroxy-3-methylpenta-1,4-dienyl)-2,2,6-trimethyl-7-oxa-b icyclo (2.2.1) heptane (VI) by conventional vinylation (or ethynylation followed by partial hydrogenation); (iv) reacting (VI) with a triaryl phosphine (preferably PPh3) and a strong acid to give a mixture of a C15 triaryl phosphonium salt of formula (III) and the isomer of formula (III'); and (v) subjecting 2 moles of the mixture to a double Wittig olefin synthesis reaction with 2,7-dimethyl-octa-2,4,6-triene-1,8-dial (VIII) to give (I). Ar = aryl (preferably optionally substituted phenyl); and X = 1 equivalent of an anion of a strong acid (preferably Cl, Br or HSO4). The preparation of (I) by step (v) is claimed per se. Also claimed are (IV) and (V) and (III') in mixtures with (III).

公开(公告)号：DE59601601D1

公开(公告)日：1999-05-12

申请号：DE59601601

申请日：1996-11-15

Applicant: BASF AG

Inventor： PAUST JOACHIM DR ,  KRIEGL WOLFGANG ,  HARTMANN HORST

IPC: C07C45/61 ,  C07C45/82 ,  C07C49/497 ,  C07B57/00

Abstract: Preparation of pure trans- and cis-4-hydroxy-2,2,6-trimethylcyclohexan-1-one of formulae (I) and (II) respectively comprises separation of a mixture of these isomers by fractional distillation in a column with 30-80 theoretical plates at 50-130 degrees C and 0.1-5 mbar.