Abstract: Optically active organic compounds are prepared starting from optically inactive reactants by means of an optically active agent which influences the course of the reaction. In particular optically active compounds having a "meso" type carbon atom undergo an intramolecular ring closure in the presence of an optically active agent to yield an optically active product having one additional ring. The present process is particularly useful in the preparation of optically active bicyclic diketones which are important intermediates in the total synthesis of steroids.
Type:
Grant
Filed:
September 14, 1976
Date of Patent:
August 22, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Zoltan George Hajos, David Richard Parrish
Abstract: Barbituric acid antigens are prepared by coupling 5- or 5,5-substituted barbituric acid to immunogenic carrier materials. In preferred embodiments, proteins are used as the carrier materials and the coupling is effected by an amide linkage between the 5-substituent of the barbituric acid and a carboxyl or amino group of the protein. The resulting antigens produce immunological effects when injected into host animals, including the formation of antibodies specific for 5- and 5,5-substituted barbituric acids. These specific antibodies are useful in bioanalytical techniques for the assay of barbituric acids in biological fluids.
Abstract: Optically active organic compounds are prepared starting from optically inactive reactants by means of an optically active agent which influences the course of the reaction. In particular optically active compounds having a "meso" type carbon atom undergo an intramolecular ring closure in the presence of an optically active agent to yield an optically active product having one additional ring. The present process is particularly useful in the preparation of optically active bicyclic diketones which are important intermediates in the total synthesis of steroids.
Abstract: A multi-step, stereospecific total synthesis of steroids utilizing intermediates having a cyanoalkyl A-ring precursor is disclosed. The initial starting materials for this process are the relatively inexpensive and commercially available reagents .gamma.-butyrolactone and sodium cyanide. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly 19-norsteroids. It is a feature of this process that conditions employed during the multiple step synthesis are selected so as to retain the normally labile nitrile group even during hydrogenation and hydrolysis steps. In this manner, it is possible to employ the nitrile group as an A-ring precursor without resorting to protective groups as was heretofore found necessary in previous steroid total synthesis processes.
Type:
Grant
Filed:
May 10, 1977
Date of Patent:
August 8, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Noal Cohen, Michael Rosenberger, Gabriel Saucy
Abstract: Optically active organic compounds are prepared starting from optically inactive reactants by means of an optically active agent which influences the course of the reaction. In particular optically active compounds having a "meso" type carbon atom undergo an intramolecular ring closure in the presence of an optically active agent to yield an optically active product having one additional ring. The present process is particularly useful in the preparation of optically active bicyclic diketones which are important intermediates in the total synthesis of steroids.
Type:
Grant
Filed:
September 14, 1976
Date of Patent:
July 25, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Zoltan George Hajos, David Richard Parrish
Abstract: A multi-step, stereospecific total synthesis of steroids is disclosed. The starting materials for this process are the relatively inexpensive and readily available m-alkoxy acetophenones. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly A-ring aromatic steroids. This process features an early optical resolution and a unique asymmetric induction which insures the correct stereochemistry of the final steroidal product.
Abstract: Aminoaryl esters and amino-lower alkyl amides of carboxy substituted barbiturates are linked via an amide linkage to carboxylated latex polymers to form reagents which are useful in a sensitive diagnostic test to detect the presence of barbiturates in body fluids.The large increase in the abuse of therapeutic agents, particularly the barbiturates, by the general population as well as military personnel, has brought with it a substantial need to improve analytical techniques for the determination of such agents in biological fluids. In many instances, medical treatment centers are faced with the immediate need for determining the identity of a barbiturate taken by a patient who is unable, being in a comatose condition, or unwilling to supply such information to the treating physician. Early procedures involved the identification of barbiturates by extraction and thin-layer, gas chromatographic and spectrophotometric methods.
Type:
Grant
Filed:
May 26, 1976
Date of Patent:
July 18, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Antonino Focella, John Edward Heveran, Sidney Teitel, Manfred Weigele
Abstract: A process for the preparation of 1.alpha.-hydroxylated cholesterol derivatives useful for the synthesis of 1.alpha.-hydroxylated cholecalciferols, is disclosed.
Abstract: A sensitive immunoassay for clonidine, 2-(2,6-dichloroanilino)-2-imidazoline hydrochloride is described. To prepare the clonidine selective antiserum, an antigen is made comprising 4-[[6-[2,4-dichloro-3(4,5-dihydro-1H-imidazol-2-yl)amino]hydroxyphenyl]azo ]benzoic acid covalently bonded to an immunogenic carrier material through a peptide bond formed from said carboxyl group and amino groups contained in said immunogenic carrier material and the antigen is injected into a suitable host animal to elicit the desired antiserum.
Abstract: A multi-step, stereospecific total synthesis of steroids is disclosed. The starting materials for this process are the relatively inexpensive and readily available m-alkoxy acetophenones. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly A-ring aromatic steroids. This process features an early optical resolution and a unique asymmetric induction which insures the correct stereochemistry of the final steroidal product.
Abstract: Dienylphosphates of the formula ##STR1## wherein each of R.sub.1 and R.sub.1 ' is lower alkyl, aryl or benzyl and each of R.sub.2, R.sub.3 and R.sub.4 is hydrogen or lower alkyl, are useful as anthelmintic agents and as intermediates for enolphosphates having anthelmintic activity.
Type:
Grant
Filed:
February 7, 1977
Date of Patent:
May 9, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Kaspar F. Burri, Frank Kienzle, Perry Rosen
Abstract: Dienylphosphates of the formula ##STR1## wherein each of R.sub.1 and R.sub.1 ' is lower alkyl, aryl or benzyl and each of R.sub.2, R.sub.3 and R.sub.4 is hydrogen or lower akyl,Are useful as anthelmintic agents and as intermediates for enolphosphates having anthelmintic activity.
Type:
Grant
Filed:
February 7, 1977
Date of Patent:
May 2, 1978
Assignee:
Hoffman-La Roche Inc.
Inventors:
Kaspar F. Burri, Frank Kienzle, Perry Rosen
Abstract: A field effect liquid crystal light shutter employing low temperature nematic liquid crystals of the p-alkylphenyl-p'-akyl and alkoxy benzoate series.
Abstract: Dienylphosphates of the formula ##STR1## wherein each of R.sub.1 and R.sub.1 ' is lower alkyl, aryl or benzyl and each of R.sub.2, R.sub.3 and R.sub.4 is hydrogen or lower alkyl,Are useful as anthelmintic agents and as intermediates for enolphosphates having anthelmintic activity.
Type:
Grant
Filed:
February 7, 1977
Date of Patent:
March 7, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Kaspar F. Burri, Frank Kienzle, Perry Rosen
Abstract: A sensitive immunoassay for acetylcholine is described. To prepare the acetylcholine selective antiserum, an antigen is made comprising 6-aminocaproic acid (2-trimethylaminoethyl) ester covalently bonded to an immunogenic carrier material through a peptide bond formed from said 6-amino group and carboxyl groups contained in said immunogenic carrier material and the antigen is injected into a suitable host animal to elicit the desired antiserum.
Abstract: Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula ##STR1## wherein m is an integer having a value of 1 or 2; R.sub.4 is hydrogen or lower alkyl; Z is lower alkylenedioxy, CH(OR.sub.2 ) and carbonyl; R.sub.8 when taken alone is hydrogen; R.sub.9 when taken alone is lower alkoxycarbonyl, aryloxy-carbonyl, lower cycloalkyloxycarbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is carbonyl R.sub.8 when taken alone is hydrogen; R.sub.9 when taken alone is carbonyl halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R.sub.
Abstract: A multi-step, stereospecific total synthesis of steroids utilizing intermediates having a cyanoalkyl A-ring precursor is disclosed. The initial starting materials for this process are the relatively inexpensive and commercially available reagents .gamma.-butyrolactone and sodium cyanide. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly 19-norsteroids. It is a feature of this process that conditions employed during the multiple step synthesis are selected so as to retain the normally labile nitrile group even during hydrogenation and hydrolysis steps. In this manner, it is possible to employ the nitrile group as an A-ring precursor without resorting to protective groups as was heretofore found necessary in previous steroid total synthesis processes.
Type:
Grant
Filed:
October 26, 1976
Date of Patent:
January 31, 1978
Assignee:
Hoffman-La Roche, Inc.
Inventors:
Noal Cohen, Michael Rosenberger, Gabriel Saucy
Abstract: An improved process for the preparation of 6,6-alkylenedioxyalkan-2-ones starting from alkyl vinyl ketones and alkyl acetoacetates is disclosed. The 6,6-alkylenedioxyalkan-2-ones are useful as intermediates in the total synthesis of therapeutically valuable steroids.
Type:
Grant
Filed:
May 3, 1976
Date of Patent:
January 10, 1978
Assignee:
Hoffmann-La Roche Inc.
Inventors:
Urs Oskar Hengartner, Pius Anton Wehrli