公开(公告)号：DE3145435A1

公开(公告)日：1983-05-26

申请号：DE3145435

申请日：1981-11-16

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  SIEGEL HARDO DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C17/093 ,  C07C43/04 ,  C07C43/12 ,  C07C43/13 ,  C07C51/235 ,  C07C51/487 ,  C07D339/08

Abstract: Compounds of the general formula in which A and B are identical or different and denote a group -S-R , in which R represents an alkyl radical, a cycloalkyl radical or an aryl radical which can be substituted by inert groups, or else both radicals R together represent an alkylene radical and R and R are different and denote either H or one of the groups in which R represents a protecting group which can be eliminated by hydrolysis or hydrogenolysis, in particular a tert.-butyl group. The novel compounds can be used advantageously as intermediates for the synthesis of vitamin E, in particular of natural, optically active vitamins.

公开(公告)号：DE3018109A1

公开(公告)日：1981-11-19

申请号：DE3018109

申请日：1980-05-12

Applicant: BASF AG

Inventor： ROSSY PHILLIP A DIPL CHEM DR ,  VOGEL FRIEDRICH DIPL CHEM DR

IPC: C07D333/36 ,  C07D495/04 ,  C07D495/06

Abstract: In the prodn. of biotin, (A) a 2-formyl-3,4- diaminothiophene (I) is subjected to Wittig reaction with a carboxypropylidene-phosphorane (II); (B) the resulting 5-(3,4-diaminothienyl)-pentenoic or -pentadienoic acid deriv. (III) is hydrogenated in a conventional manner; (C) the protecting groups R1-R4 are removed from the resulting tetrahydrothiophene deriv. (IV) by saponification or hydrogenolysis. and (D) if necessary the intermediately formed diamine deriv. is converted into biotin by reaction with phosgene. In the formulae R1-R4 are H or a usual amino-protecting group removable by acidic or basic hydrolysis or hydrogenolysis; or R1 and R3 together represent a carbonyl group; and R5 is lower alkyl, triarylsilyl or acyl. Biotin (vitamin H) is essential for human nutrition. The hydrogenation steps give an all-cis product, so that racemic biotin is obtd. free from other diastereomers.

公开(公告)号：DE3145408A1

公开(公告)日：1983-05-26

申请号：DE3145408

申请日：1981-11-16

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  SIEGEL HARDO DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C51/235 ,  C07C51/487 ,  C07C59/125

Abstract: The novel optically active compounds (2R)-3-tert-butoxy-2- methylpropanoic acid and (2S)-3-tert-butoxy-2-methylpropanoic acid can be obtained in an advantageous manner by resolution of the racemic acid with chiral bases. They are thus industrially relatively easily accessible, optically active building blocks which can be used for the synthesis of desired optically active active substances, for example natural vitamin E.

公开(公告)号：DE3018388A1

公开(公告)日：1981-11-19

申请号：DE3018388

申请日：1980-05-14

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR ,  NUERRENBACH AXEL DIPL CHEM DR

IPC: C07C69/67 ,  B01J31/00 ,  B01J31/28 ,  C07C29/00 ,  C07C29/10 ,  C07C29/147 ,  C07C41/00 ,  C07C43/315 ,  C07C45/00 ,  C07C47/12 ,  C07C47/19 ,  C07C47/198 ,  C07C59/76 ,  C07C67/00 ,  C07C69/12 ,  C07D307/33 ,  C07D307/60 ,  C07D311/72 ,  C07D315/00 ,  C07D319/06 ,  C07B1/00 ,  C07C59/325 ,  C07D307/32

公开(公告)号：DE3322995A1

公开(公告)日：1983-12-29

申请号：DE3322995

申请日：1983-06-25

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR ,  NUERRENBACH AXEL DIPL CHEM DR

IPC: C07D311/72 ,  C07F3/02 ,  C07F9/143 ,  C07F9/54 ,  C07F9/40

Abstract: Compounds of the general formula I in which R denotes H, an alkyl radical, arylalkyl radical or an aliphatic acyl radical, preferably a benzyl group or acetyl group, and Y represents OH and X represents H (Ia) or else X and Y together represent a further bond between the C atoms carrying X and Y (Ib) and the dashed line may denote an additional bond, in particular [2R,1'Z,3'E,7'E]-6-benzyloxy-2,5,7,8-tetramethyl-2-(4',8',12'- trimethyltrideca-1',3',7'-trien-1'-yl)chroman and 6-benzyloxy-2,5,7,8- tetramethyl-2-(1'-hydroxy-4',8',12'-trimethyltrideca-3',7'-dien-1-yl)- chroman, and compounds of the general formula II in which Z represents one of the groups ClMg-; BrMg- (IIa); CL ; BR - (IIb> in which R represents alkyl having 1 to 4 C atoms, in particular (3,7,11-trimethyltrideca-2,6,10-trien-1-yl)triphenylphosphonium chloride and dimethyl (3,7,11-trimethyltrideca-2,6,10-trien-1-yl)- phosphite. The invention furthermore relates to a process for the preparation of (2R,4'RS,8'RS)- alpha -tocopherol or (all-rac)- alpha -tocopherol, starting from the compounds of the formula II and via the compounds of the formula I.

公开(公告)号：DE3150723A1

公开(公告)日：1983-06-30

申请号：DE3150723

申请日：1981-12-22

Applicant: BASF AG

Inventor： TRAUTMANN WALTER DIPL CHEM DR ,  VOGEL FRIEDRICH DIPL CHEM DR

IPC: C07D233/32 ,  C07D233/34 ,  C07D233/26

Abstract: A process for the preparation of 1,3-disubstituted 4,5-cis-dicarboxy-2-imidazolidones useful as intermediates in the preparation of Vitamin H (biotin), said intermediates have the general formula in which R is an aliphatic hydrocarbon radical having 1 to 8 carbon atoms, an aralkyl radical or an aromatic hydrocarbon radical, preferably an allyl radical or a benzyl radical, comprising reacting a defined diaminosuccinic acid with phosgene in the presence of an alkali metal hydroxide.

公开(公告)号：DE3145486A1

公开(公告)日：1983-05-19

申请号：DE3145486

申请日：1981-11-16

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C17/00 ,  C07C17/16 ,  C07C17/26 ,  C07C17/354 ,  C07C19/01 ,  C07C19/075 ,  C07C31/36 ,  C07C45/40 ,  C07C47/14 ,  C07C51/16 ,  C07C51/56 ,  C07C55/02 ,  C07D315/00 ,  C07C69/63 ,  C07C19/02 ,  C07C67/00

Abstract: Novel optically active alkyl 5-chloro- and 5-bromo-3-methylpentanoates of the general formula I in which Y represents Cl or Br and R represents a lower alkyl radical, a process for their preparation which is characterised in that an optically active 3-methylpentane-1,5-dioic acid monoalkyl ester of the general formula II in which R has the abovementioned meaning, is converted into an optically active 3-methylvalerolactone by selective reduction of the acid group or by selective reduction of the ester group and this lactone is treated at 0 to 50 DEG C with a solution of hydrogen chloride or hydrogen bromide in an alkanol ROH, and their use as optically active intermediates for the preparation of the C15-building blocks required for the synthesis of the side chain of (R,R,R)- alpha -tocopherol, and a process for the preparation of (3R,7R)-1-chloro- and (3R,7R)-1-bromo-3,7,11-trimethyldodecane starting from (R)-5-chloro- and (R)-5-bromo-3-methylpentanoic esters.

公开(公告)号：DE3145454A1

公开(公告)日：1983-05-26

申请号：DE3145454

申请日：1981-11-16

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C17/093 ,  C07C17/26 ,  C07C19/01 ,  C07C19/075 ,  C07C53/19 ,  C07D315/00 ,  C07C19/02 ,  C07C59/19

Abstract: 1-Bromo-4-chloro-2-methylbutane, (S)-1-bromo-4-chloro- 2-methylbutane (V) and (R)-5-chloro-3-methylpentanoic acid (Va) and the use of (S)-3-methylvalerolactone, (S)-1-bromo-4-chloro- 2-methylbutane (V) or (R)-5-chloro-3-methylpentanoic acid (Va) as optically active intermediates for the synthesis of the side chain of (R,R,R)- alpha -tocopherol and a process for the preparation of (3R,7R)-1-chloro-3,7,11-trimethyldodecane of the formula Ia in which n is 1, characterised in that A) (S)-3-methylvalerolactone of the formula IV is cleaved using liquid hydrogen chloride at 100 to 170 DEG C in a pressurised vessel to give the novel (3R)-5-chloro-3-methylpentanoic acid of the formula Va B) this acid is converted in a manner known per se into the novel dihalide of the formula IIa in which X represents Br or I, by decarboxylation with bromine or iodine, and C) this dihalide is reacted in the presence of copper ions with an organomagnesium compound of the formula IIIa in which Y represents Cl, Br or I and n represents 1, at temperatures below 0 DEG C in an ether solvent, preferably tetrahydrofuran.

公开(公告)号：DE3145485A1

公开(公告)日：1983-05-19

申请号：DE3145485

申请日：1981-11-16

Applicant: BASF AG

Inventor： VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C29/32 ,  C07C33/025 ,  C07C45/40 ,  C07D309/10

Abstract: (R)-3,7-Dimethyl-5-octen-1-ol of the formula I its use as optically active intermediate for the synthesis of the side chain of (R,R,R)- alpha -tocopherol and a process for its preparation which is characterised in that A) (3S)-3-methylvalerolactone of the formula II is reduced in a manner known per se to (4S)-2-hydroxy-4-methyltetrahydropyran of the formula III and B) this tetrahydropyran is reacted with a phosphorus ylide of the general formula IV in which Ar represents identical or different aryl radicals or cyclohexyl radicals, preferably phenyl or tolyl, in a Wittig reaction.

公开(公告)号：DE3139238A1

公开(公告)日：1983-04-21

申请号：DE3139238

申请日：1981-10-02

Applicant: BASF AG

Inventor： ERNST HANS-GEORG DIPL CHEM DR ,  VOGEL FRIEDRICH DIPL CHEM DR ,  PAUST JOACHIM DIPL CHEM DR

IPC: C07C17/16 ,  B01J27/122 ,  C07B61/00 ,  C07C17/00 ,  C07C17/26 ,  C07C17/263 ,  C07C19/01 ,  C07C19/075 ,  C07C29/147 ,  C07C29/40 ,  C07C51/363 ,  C07C51/487 ,  C07C53/19 ,  C07C67/00 ,  C07D311/72 ,  C07C19/02

Abstract: (2R,6R)-1-Chloro-2,6,10-trimethyl-undecane I, (R)-(+)- beta -chloro-isobutyric acid II, (S)-(+)-1-bromo-3-chloro-2-methylpropane IV and (2R)-(+)-1-chloro-2,6-dimethyl-heptane V are novel optically active units for the synthesis of the side chain of (R,R,R)- alpha -tocopherol. In the process according to the invention, the optically active C14-chloride I is obtained in 6 simple reaction steps starting from II, via the novel intermediates IV and V, in accordance with the following equation: (II) (III) (IV) (V) (VI) &bhbrace& (VII) + (IV) (I)