-
公开(公告)号:DE3705785A1
公开(公告)日:1988-09-01
申请号:DE3705785
申请日:1987-02-24
Applicant: BASF AG
Inventor: KNAUS GUENTER H DR , PAUST JOACHIM DR
IPC: B01J31/30 , C07B61/00 , C07C45/00 , C07C45/38 , C07C47/21 , C07C47/225 , C07C47/267 , C07C47/277 , C07C49/757 , C07C67/00 , C07C67/31 , C07C67/313 , C07C69/73 , C07C69/738 , C07C401/00 , C07C403/00 , C07C403/08 , C07C403/14 , C07D317/26 , C07D319/06 , C07C175/00
Abstract: A process for the preparation of polyene aldehydes of the formula I … … in which R represents … … where R' has the meaning alkyl, aryl, aralkyl or cycloalkyl and, if desired, can be further substituted and the radicals R'' represent C1-C4-alkyl or together denote -CH2-CH2- or -CH2-CH2-CH2- bridges which, if desired, can be further substituted by C1-C4-alkyl,… by catalytic oxidation of the corresponding polyene alcohol with oxygen or an oxygen-containing gas is proposed, characterised in that the oxidation is carried out in the presence of the catalyst system 2,2,6,6-tetramethylpiperidin-1-oxyl or 4-oxo- 2,2,6,6-tetramethylpiperidin-1-oxyl and copper(I) chloride.
-
公开(公告)号:DE3869335D1
公开(公告)日:1992-04-23
申请号:DE3869335
申请日:1988-11-11
Applicant: BASF AG
Inventor: KUEKENHOEHNER THOMAS DR , GOETZ NORBERT DR , THEOBALD HANS DR , KNAUS GUENTER H DR
IPC: C07D213/48 , C07D213/50 , C07D239/26 , C07D261/08
Abstract: Prodn. of heteroaromatic aldehydes or ketones of formula R-CO-R1 (I) is effected by oxidising the corresp. 1-hydroxyalkyl cpds. of formula R-C(OH)H-R1 (II) with an (in)organic hypochlorite or hypobromite in the presence of an oxidised tetraalkyl cyclic amine (III): R=5 or 6-membered heteroaryl contg. N atom R1=H or 1-20C alkyl. (III) is of formula (III): A1-A4=1-4C alkyl; Q=a gp. of formula Q1-Q3= X=an anion; n=0 or 1; Y=O, CO or CR2R3; R2 and R3=H, OH, or C- or O-bonded organic gps. opt. linked to form a 5- or 6-membered ring. Pref. R=opt. substd. isoxazolyl, pyridyl or pyrimidinyl.
-
公开(公告)号:DE3738909A1
公开(公告)日:1989-05-24
申请号:DE3738909
申请日:1987-11-17
Applicant: BASF AG
Inventor: KUEKENHOEHNER THOMAS DR , GOETZ NORBERT DR , THEOBALD HANS DR , KNAUS GUENTER H DR
IPC: C07D213/48 , C07D213/50 , C07D239/26 , C07D261/08
-
公开(公告)号:DE3719622A1
公开(公告)日:1988-12-29
申请号:DE3719622
申请日:1987-06-12
Applicant: BASF AG
Inventor: KNAUS GUENTER H DR , ERNST HANSGEORG DR , THYES MARCO DR , PAUST JOACHIM DR
IPC: C07C69/65 , C07C69/653 , C07F9/40
Abstract: Alkyl gamma -halotiglates of the general formula I (I) where X is Cl or Br and R2 is alkyl of 1 to 3 carbon atoms, having a high E isomer content, are prepared by a process in which (a) the corresponding 2-methyl-but-3-enoate of the general formula II (II) is reacted with chlorine or bromine in the absence of a solvent and (b) the resulting 2-methyl-3,4-dihalobutyrate of the general formula III (III) is dehydrohalogenated by reaction with a solution of an alkali metal hydroxide in an alcohol R2OH, where R2 has the stated meaning, or in a mixture of water and an alcohol R2OH, and the products are further processed to give O,O-dialkyl- gamma -phosphonotiglates of the general formula IV (IV) where R1 is alkyl of 1 to 4 carbon atoms and R2 is alkyl of 1 to 3 carbon atoms, preferably ethyl, by reaction with a trialkyl phosphite and thermal isomerization. The process gives C5 building blocks which are extremely interesting for polyene chemistry, the said building blocks being obtained in good yields and essentially in the form of the required E isomers.
-
公开(公告)号:DE3877423D1
公开(公告)日:1993-02-25
申请号:DE3877423
申请日:1988-06-08
Applicant: BASF AG
Inventor: KNAUS GUENTER H DR , ERNST HANSGEORG DR , THYES MARCO DR , PAUST JOACHIM DR
IPC: C07C69/65 , C07C69/653 , C07F9/40
Abstract: Ethyl 4-(O,O-dialkylphosphono) tiglates of formula (Ia) are new (where R1 = 1-4C alkyl). Tiglates (I) are produced by (a) reacting an alkyl 2-methyl-3-butenoate of formula (II) with Cl2 or Br2 in the absence of solvent; (b) reacting the resulting 3,4-dihalo-2-methylbutyrate of formula (III) with an alkali metal hydroxide in R2OH or R2OH/H2O; (c) reacting the resulting alkyl 4-halotiglate (E/Z isomer mixt.) of formula (IV) with a trialkyl phosphite of formula (V); and (d) thermally isomerising the prod. (In the formulae R2 = 1-3C alkyl; X = Cl or Br). Prodn. of cpds. (IV) is also claimed.
-
公开(公告)号:DE3872002D1
公开(公告)日:1992-07-23
申请号:DE3872002
申请日:1988-02-20
Applicant: BASF AG
Inventor: KNAUS GUENTER H DR , PAUST JOACHIM DR
IPC: B01J31/30 , C07B61/00 , C07C45/00 , C07C45/38 , C07C47/21 , C07C47/225 , C07C47/267 , C07C47/277 , C07C49/757 , C07C67/00 , C07C67/31 , C07C67/313 , C07C69/73 , C07C69/738 , C07C401/00 , C07C403/00 , C07C403/08 , C07C403/14 , C07D317/26 , C07D319/06
Abstract: Prodn. of polyene-aldehydes of formula (I) comprise oxidn. of the corresponding polyene-alcohol (II) with O2 (contg. gas) in presence of a catalyst system consisting of 2,2,6,6-tetramethyl piperidin-1-oxyl (III), or its 4-oxo deriv., and CuCl. (a), (b), (c), (d) COOR', CHO or CH(OR'')2; R' = opt. substd. alkyl, aryl, aralkyl or cycloalkyl, all opt. substd.; R'' = 1-4C alkyl or 2 R'' are together CH2CH2 or CH2CH2CH2, opt. substd. by 1-4C alkyl. Pref. (I) is (all-E) retinal (Ia), prepd. from (all-E) retinol (IIa), and reaction is carried out in a homogeneous soln.. Reaction solvents include DMF; dimethylacetamide; N-methyl-2-pyrrolidone or N,N-dimethyl-(ethylene or propylene)ureas, and the reaction is at 0-40 (pref. 20-40) deg.C. The (III):CuCl mole ratio is 1:0.5-3, and the individual catalyst components are 1-10 (esp. 5-10) mole % based on (II).
-
-
-
-
-