Cyclopropyl Patents (Class 562/506)
  • Patent number: 4609673
    Abstract: The present invention provides carboxylic acid derivatives of the general formula: ##STR1## wherein R is a hydrogen atom, alkyl, a metal cation or an ammonium or alkylammonium ion, R.sub.1 is a hydrogen atom, a hydroxyl group or an alkyl, O-alkyl,O-benzyl or O-acyl radical, R.sub.2 is a hydrogen atom or an alkyl, aryl or aralkyl radical, n is 0, 1 or 2 and R.sub.
    Type: Grant
    Filed: December 18, 1984
    Date of Patent: September 2, 1986
    Assignee: Boehringer Mannheim GmbH
    Inventors: Hermann Eggerer, Bernd Hagenbruch, Tran G. Nguyen, Karlheinz Stegmeier, Johannes Pill
  • Patent number: 4599439
    Abstract: Analogs of arachidonic acid are provided having the structure ##STR1## wherein R is CH.sub.2 OH or CO.sub.2 H and m is 1 or 2. These compounds are useful as inhibitors of leukotriene and prostaglandin biosynthesis and as such are useful an antiallergy and antiinflammatory agents.
    Type: Grant
    Filed: August 6, 1984
    Date of Patent: July 8, 1986
    Assignee: E. R. Squibb & Sons, Inc.
    Inventor: Raj N. Misra
  • Patent number: 4599444
    Abstract: The invention relates to a new process for separating the four stereoisomers of the cyclopropanecarboxylic acids of the formula ##STR1## wherein R stands for a methyl group or a halogen atom.
    Type: Grant
    Filed: February 17, 1984
    Date of Patent: July 8, 1986
    Assignee: Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Rt.
    Inventors: Elemer Foggassy, Ferenc Faigl, Rudolf Soos, Jozsef Rakoczi
  • Patent number: 4571345
    Abstract: Compounds of the formula: ##STR1## wherein n is 0 or 1, R is lower alkyl (substituted or unsubstituted), R' is H or lower alkyl, and R" is a branched alkyl, alkyl-cycloalkyl, cycloalkyl, polycycloalkyl (poly=2 or more, fused or non-fused), phenyl or alkyl-substituted phenyl, and physiologically acceptable cationic and acid addition salts thereof, which compounds are potent sweeteners. These derivatives of gem-diaminoalkanes are many times sweeter than sugar and are free from undesirable flavor qualities. Furthermore, they possess an unanticipated high degree of solubility compared with known synthetic sweeteners. In addition, the compounds possess high stability so that they can be used in all types of beverages and in conventional food processing. Sweetening compositions and sweetened edible compositions of these compounds are also provided.
    Type: Grant
    Filed: June 13, 1983
    Date of Patent: February 18, 1986
    Assignee: Cumberland Packing Corp.
    Inventors: Michael S. Verlander, William D. Fuller, Murray Goodman
  • Patent number: 4570014
    Abstract: Novel plant growth regulant composition comprising as an active ingredient at least one cycloalkanecarboxylic acid compound of the formula ##STR1## in which R is hydroxyl, alkoxy, aralkoxy, amino, alkylamino, dialkylamino or the radicalO.sup..crclbar. M.sup..sym.whereinM.sup..sym. is one alkali metal ion equivalent or alkaline earth metal ion equivalent, or an ammonium, alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium ion,R.sup.1 is amino or the radical ##STR2## wherein R.sup.2 is hydrogen, alkyl or aryl, orR.sup.1 is the radical --N.sup..sym. H.sub.3 X.sup..crclbar.,wherein X.sup.63 is chloride, bromide or iodide, and n is 1, 2, 3, 4 or 5,in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
    Type: Grant
    Filed: December 15, 1981
    Date of Patent: February 11, 1986
    Assignee: Bayer Aktiengesellschaft
    Inventors: Rolf Schroder, Klaus Lurssen
  • Patent number: 4562006
    Abstract: Cycloheptadiene analogues of arachidonic acid as well as their cyclopropyl intermediates are described as inhibiting human leukocyte lipoxygenase and antagonizing SRS-A. Methods of manufacture and pharmaceutical compositions are described. The compounds are useful in treating allergic diseases, cardiovascular diseases and immunoinflammatory diseases.
    Type: Grant
    Filed: January 11, 1984
    Date of Patent: December 31, 1985
    Assignee: Warner-Lambert Company
    Inventors: David T. Connor, Roderick J. Sorenson
  • Patent number: 4542235
    Abstract: A method for producing an optically active 2,2-dimethylcyclopropanecarboxylic acid useful as an intermediate for dehydropeptidase I inhibitors, medicines and agricultural chemicals, which comprises reacting an optically active diphenylethylamine represented by the formula, ##STR1## wherein R.sub.1 and R.sub.2 are each a hydrogen atom or a lower alkyl group, with 2,2-dimethylcyclopropanecarboxylic acid in a solvent to achieve the optical purification of said acid.
    Type: Grant
    Filed: April 5, 1983
    Date of Patent: September 17, 1985
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masayoshi Minai, Tadashi Katsura, Kazuhiko Hamada, Gohfu Suzukamo
  • Patent number: 4537723
    Abstract: The present invention provides novel derivatives of leukotrienes A and C which are useful in inhibiting the smooth muscle contracting effects of SRS-A; inhibiting platelet aggregation; and inhibiting the biosynthesis of thromboxane A.sub.2.
    Type: Grant
    Filed: October 24, 1983
    Date of Patent: August 27, 1985
    Assignee: The Upjohn Company
    Inventor: William P. Schneider
  • Patent number: 4537897
    Abstract: Novel 3-(1,2-propadienyl)-cyclopropane-carboxylates of the formula ##STR1## wherein R is alcohol used in pyrethrinoid synthesis, X and Y are both hydrogen or individually halogen or X is hydrogen or halogen and Y is alkyl of 1 to 18 carbon atoms or halogen or X is hydrogen or halogen or alkyl of 1 to 18 carbon atoms and Y is --COOR' or --CN or ##STR2## R' is alkyl of 1 to 18 carbon atoms, R.sub.2 and R.sub.3 are individually hydrogen or alkyl of 1 to 18 carbon atoms or R.sub.2 and R.sub.3 together with the nitrogen atom form a heterocycle having pesticidal properties.
    Type: Grant
    Filed: September 15, 1983
    Date of Patent: August 27, 1985
    Assignee: Roussel Uclaf
    Inventors: Jean Tessier, Jean-Pierre Demoute, Joseph Cadiergue
  • Patent number: 4528397
    Abstract: An aminocarboxylic acid derivative represented by the formula ##STR1## wherein R.sub.1 and R.sub.2, independently from each other, represent a hydrogen atom or an alkyl group which may have a substituent, and Y represents --NH-- or --S--, provided that when Y represents --NH--, at least one of R.sub.1 and R.sub.2 represents an alkyl group which may have a substituent. These compounds have excellent inhibitory activity on dipeptidase in animals, and are useful for administration in combination with carbapenem antibiotics.
    Type: Grant
    Filed: March 29, 1983
    Date of Patent: July 9, 1985
    Assignee: Sanraku-Ocean Co., Ltd.
    Inventors: Norio Shibamoto, Takeo Yoshioka, Yasuo Fukagawa, Tomoyuki Ishikura
  • Patent number: 4526987
    Abstract: Lactones of the formula ##STR1## wherein R is hydrogen or a CX.sub.3 group, and each X is a chlorine or bromine atom, are converted to the known cis-3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylic acids or lower alkyl esters, from which pyrethroid insecticides are obtained.
    Type: Grant
    Filed: January 3, 1979
    Date of Patent: July 2, 1985
    Assignee: FMC Corporation
    Inventors: Kiyoshi Kondo, Toshiyuki Takashima, Daiei Tunemoto
  • Patent number: 4518797
    Abstract: Compounds of the formula ##STR1## wherein R.sup.1 is an acyl group or certain optionally halo-substituted hydrocarbyl groups, and X is --CH.sub.2 CH(OCH.sub.3).sub.2, --CH.sub.2 CHO, --CH.dbd.CHOR.sup.2 in which R.sup.2 is acyl, --CHO,--C(O)Cl, --C(O)Br or --C(O)OR in which R is H, a salt-forming cation, an alkyl group or the residue of a pyrethroid alcohol are new pesticides or intermediates therefore. The compounds are prepared using a multi-step synthesis starting from the natural terpene, 3-carene.
    Type: Grant
    Filed: March 15, 1979
    Date of Patent: May 21, 1985
    Assignee: Shell Oil Company
    Inventor: Steven A. Roman
  • Patent number: 4513147
    Abstract: Novel lactones of 2,2-dimethyl-cyclopropane-1-carboxylic acids of the formula ##STR1## wherein X.sub.1, X.sub.2 and X.sub.
    Type: Grant
    Filed: March 30, 1981
    Date of Patent: April 23, 1985
    Assignee: Roussel Uclaf
    Inventors: Jacques Martel, Jean Tessier, Jean-Pierre Demoute, Jean Jolly
  • Patent number: 4510321
    Abstract: Processes for the autoxidative cleavage of selected ketones such as C.sub.4 -C.sub.10 cycloalkanones having at least one hydrogen or at least one R group on a carbon alpha to the carbonyl carbon or aryl alkyl ketones having the formula III ##STR1## comprising contacting a liquid phase comprising said ketone with elemental oxygen gas, preferably air, in the presence of a pulverized alkali metal hydroxide at a temperature of no more than 50.degree. C. for a time sufficient to produce an oxidized product are disclosed. Preferred cycloalkanones, 2-alkyl- and 2-arylcyclohexanone are autoxidized in pulverized sodium hydroxide/dimethoxyethane to produce 6-alkyl- or 6-aryl-6-oxohexanoic acids, respectively.
    Type: Grant
    Filed: January 31, 1983
    Date of Patent: April 9, 1985
    Assignee: Allied Corporation
    Inventors: Divakaran Masilamani, Edward H. Manahan
  • Patent number: 4508919
    Abstract: The invention relates to a process for the preparation of enantiomers of trans vinyl-cyclopropane carboxylic acids of the formula I, ##STR1## wherein R is a methyl group or chlorine atom, by resolution of racemic trans compound or mixture of racemic cis and trans compounds by using (+)- or (-)-N-(1-formamido-2,2,2-trichloroethyl)-piperazine as a resolving agent in a polar solvent then separating the crystallizing salt of (+)-trans carboxylic acid and (-)-resolving agent or (-)-trans carboxylic acid and (+)-resolving agent from the mother liquor by filtration and obtaining the enantiomers by acidifying the mother liquor or the salts suspended in water followed by extraction with a solvent and evaporation.The products so obtained may be used as starting materials for the preparation of insecticides.
    Type: Grant
    Filed: November 25, 1983
    Date of Patent: April 2, 1985
    Assignee: Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Rt.
    Inventors: Elemer Fogassy, Laszlo Toke, Ferenc Faigl, Rudolf Soos, Jozsef Bozzay, Rezso Kolta, Jozsef Nemes, Peter Bencsik
  • Patent number: 4504671
    Abstract: Aldoxime or ketoxime-O-alkanoic acid is prepared by transoximation of an aldehyde or ketone, the reaction being conducted in a liquid phase at a pressure below one atmosphere. Conversion of the aldoxime or ketoxime-O-alkanoic acid to the ester or salt form is also described.
    Type: Grant
    Filed: October 15, 1982
    Date of Patent: March 12, 1985
    Assignee: PPG Industries, Inc.
    Inventors: Dennis K. Krass, John C. Crano, Melvin S. Newman
  • Patent number: 4500733
    Abstract: A cyclopropanecarboxylic acid of the formula ##STR1## is prepared by the reaction of a compound of the formula ##STR2## with an alkali metal hydroxide or alkaline earth metal hydroxide in an ether type solvent. R.sup.1, R.sup.2, and R.sup.4 each independently is hydrogen or a hydrocarbon residue, R.sup.3 is hydrogen or lower alkyl, X is halogen, and A is --CH.sub.2 --CX, 3 or --CH.dbd.CX.sub.2.
    Type: Grant
    Filed: February 14, 1983
    Date of Patent: February 19, 1985
    Assignee: Sagami Chemical ResearchCenter
    Inventors: Kiyoshi Kondo, Kiyohide Matsui
  • Patent number: 4492800
    Abstract: A process for the preparation of a 1,1-dichloro-alkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or together are alkanediyl,in the presence of at least an equimolar amount of magnesium. Advantageously,R.sup.1 is hydrogen,R.sup.2 is a C.sub.2 to C.sub.5 alkenyl radical or a radical of the formula ##STR4## Z is a cyano, acetal, carboxyl or C.sub.1 to C.sub.4 alkoxycarbonyl radical, or a radical of the formula COOM, andM is sodium or potassium,R.sup.3 each individually is a C.sub.1 to C.
    Type: Grant
    Filed: February 22, 1983
    Date of Patent: January 8, 1985
    Assignee: Bayer Aktiengesellschaft
    Inventors: Fritz Maurer, Uwe Priesnitz, Hans-Jochem Riebel
  • Patent number: 4492799
    Abstract: Novel halo-4-alkenoic acid compounds which are useful intermediates for the synthesis of insecticides and miticides.
    Type: Grant
    Filed: July 2, 1979
    Date of Patent: January 8, 1985
    Assignee: Union Carbide Corporation
    Inventor: Thomas N. Wheeler
  • Patent number: 4485257
    Abstract: The present invention is to provide the process for preparing racemized cyclopropanecarboxylic acids or their acid anhydrides from the corresponding optically active, particularly levo-rotatory, cyclopropanecarboxylic acid anhydrides. The racemization is effected by the treatment of the optically active acid anhydride with a Lewis acid. Thus, the present racemization process enables more efficient commercial production of dextro-rotatory cyclopropanecarboxylic acids, which are the more effective acid component of pyrethroidal insecticides, when combined with an optical resolution process.
    Type: Grant
    Filed: March 18, 1982
    Date of Patent: November 27, 1984
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Gohfu Suzukamo, Masami Fukao
  • Patent number: 4479005
    Abstract: A process has been discovered for selective preparation of isomers and enantiomers of 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane carboxylic acids. In this process an adduct of an alkyl 3,3-dimethyl-4-pentenoate and a substituted 2-oxazolidone is reacted with a substituted dihalomethane compound. The resulting compound is cyclized, dehydrohalogenated and hydrolyzed to yield the desired product. These cyclopropane carboxylic acids are useful precursors for pyrethroid insecticides.
    Type: Grant
    Filed: December 16, 1982
    Date of Patent: October 23, 1984
    Assignee: The Dow Chemical Company
    Inventor: William A. Kleschick
  • Patent number: 4473703
    Abstract: A process for isomerization of cis-chrysanthemate esters by contacting a chrysanthemate ester containing a cis-chrysanthemate ester with a Lewis acid, to transform the cis-chrysanthemate ester into trans-chrysanthemate ester through epimerization at C.sub.3 -position. The starting cis-chrysanthemate ester may be of any optical isomer ratio form (+)-form to (-)-form, including racemic form. Accordingly the process is effectively employable for the preparation of a (+)-trans-chrysanthemate ester from the (+)-cis-chrysanthemate ester. Combinations of the process with optical resolution would make the commercial production of (+)-trans-chrysanthemic acid more effective, the latter being an important acid component of pyrethroidal insecticides.
    Type: Grant
    Filed: March 18, 1982
    Date of Patent: September 25, 1984
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Gohfu Suzukamo, Masami Fukao
  • Patent number: 4473706
    Abstract: Cyclic-keto-acids of the general formula: ##STR1## wherein R is hydrogen or a monovalent alkyl radical which can be either straight chain or branched having from 1 to about 20 carbon atoms and X=1, 3, or 4, are prepared by reacting a functionalized 1-bromoalkane of the formula: ##STR2## wherein R and X are as defined above and Y is a leaving group, preferably the halogens, in a liquid solvent medium with carbon monoxide at elevated temperature and pressure in the presence of a catalytic amount of a metal carbonyl compound and an alkali or an alkaline earth metal inorganic base.
    Type: Grant
    Filed: August 6, 1982
    Date of Patent: September 25, 1984
    Assignee: Ethyl Corporation
    Inventors: John Y. Lee, Thomas J. Walter
  • Patent number: 4463188
    Abstract: A method for racemization of optically active 2,2-dimethylcyclopropane-1-carboxylic acid by converting said acid to the corresponding halide thereof represented by the general formula; ##STR1## wherein X is a halogen atom, which is heated to a temperature of about 80.degree. C. to about 300.degree. C., preferably about 100.degree. C. to about 200.degree. C., and then, if desired, producing 2,2-dimethylcyclopropane-1-carboxylic acid by hydrolysis of the resultant acid halide.
    Type: Grant
    Filed: April 4, 1983
    Date of Patent: July 31, 1984
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Gohfu Suzukamo, Masami Fukao, Yukio Yoneyoshi
  • Patent number: 4458090
    Abstract: Novel .gamma.-lactone derivatives are provided. These lactone derivatives, when reacted with hydrogen halide in alcohol, yield .gamma.-halogeno-.delta.-unsaturated carboxylic acid esters. This ring-opening process is useful for the purpose of increasing the yield of pyrethrin analogs which are of value as insecticides and agricultural chemicals. Thus, the .gamma.-lactone derivatives by-produced in the production process for dihalogenovinyl chrysanthemumates are caused to undergo ring-opening reaction to yield the corresponding .gamma.-halogeno-.delta.-unsaturated carboxylic acid esters which are important intermediates for said pyrethrin analogs.
    Type: Grant
    Filed: October 15, 1981
    Date of Patent: July 3, 1984
    Assignee: Kuraray Co., Ltd.
    Inventors: Mori Fumio, Omura Yoshiaki, Nishida Takashi, Itoi Kazuo
  • Patent number: 4448986
    Abstract: (1R,cis)-Oxyimino-substituted cyclopropanecarboxylic acids are prepared via a (1R,4R,5S)-2-acetoxy-6,6-dimethyl-4-oxo-3-oxabicyclo[3.1.0]hexane intermediate.
    Type: Grant
    Filed: July 14, 1982
    Date of Patent: May 15, 1984
    Assignee: Shell Oil Company
    Inventor: Steven A. Roman
  • Patent number: 4447637
    Abstract: A novel process for the epimerization of alkyl trans chrysanthemates comprising reacting at a low temperature in an anhydrous organic solvent an alkyl trans chrysanthemate of the formula ##STR1## of the 1S, trans or 1R, trans configuration wherein R is alkyl of 1 to 6 carbon atoms with a strong alkali metal base to obtain a compound of the formula ##STR2## wherein R has the above definition and M is an alkali metal, reacting the latter compound with a reactant of the formulaY--Awherein A is selected from the group consisting of chlorine, bromine, iodine and anion derived from a hydrogen acid and Y is an organic radical capable of forming a ketal of a ketene to obtain a compound of the formula ##STR3## reacting the latter at a low temperature in an anhydrous organic solvent with a proton donor to obtain a mixture of the corresponding alkyl cis chrysanthemate and alkyl trans chrysanthemate and recovering the cis chrysanthemic acid of the formula ##STR4## with the 1R, cis or 1S, cis configuration.
    Type: Grant
    Filed: February 9, 1982
    Date of Patent: May 8, 1984
    Assignee: Roussel Uclaf
    Inventors: Jacques Martel, Jean Buendia, Jeanine Nierat
  • Patent number: 4446077
    Abstract: Novel 2-vinyl- and 2-ethyl-cyclopropyl sulfones are provided. In addition to the ethyl or vinyl group at the 2-position of the ring, the compounds of this invention are disubstituted at the 1-position with a sulfonyl group and an acyl, nitrile or nitrile-derived radical. The sulfones of this invention are useful chemical intermediates from which a wide variety of pesticidal, herbicidal or biologically active compounds can be prepared and are useful monomers for anionic or radical polymerizations.
    Type: Grant
    Filed: February 4, 1982
    Date of Patent: May 1, 1984
    Assignee: National Distillers and Chemical Corporation
    Inventors: Richard G. Fayter, Jr., Allen L. Hall
  • Patent number: 4442099
    Abstract: A compound of the formula ##STR1## wherein n is an integer from 2 to 4; m is an integer from 3 to 5; R is OM, OR.sub.1 or NR.sub.2 R.sub.3 where M is a pharmaceutically acceptable cation;R.sub.1, R.sub.2 and R.sub.3 are the same or different and selected from the group consisting of hydrogen, C.sub.1 -C.sub.12 branched, unbranched or cyclic alkyl, aryl and aralkyl; or R.sub.2 and R.sub.3 taken together form a group of the formula ##STR2## can be used as an inhibitor of the lipoxygenase pathway of the arachidonic acid cascade in animals.
    Type: Grant
    Filed: November 27, 1981
    Date of Patent: April 10, 1984
    Assignee: Research Corporation
    Inventors: Kyriacos C. Nicolaou, Nicos A. Petasis, Steven P. Seitz
  • Patent number: 4435597
    Abstract: A process for the preparation of caronaldehyde acid or a derivative thereof of the formula ##STR1## in which R is O.sup.- Me.sup.+, or OH, andMe.sup.+ is an equivalent of an alkali metal, alkaline earth metal or ammonium cation, comprising reacting a 2-halogeno-3,3-dimethyl-5,5-dichloropentanoic acid halide of the formula ##STR2## wherein X and Y each independently is a halogen atom, with a base in the presence of water.
    Type: Grant
    Filed: March 5, 1982
    Date of Patent: March 6, 1984
    Assignee: Bayer Aktiengesellschaft
    Inventor: Dieter Arlt
  • Patent number: 4431835
    Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) chromium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.
    Type: Grant
    Filed: July 6, 1981
    Date of Patent: February 14, 1984
    Assignee: Rhone-Poulenc Industries
    Inventors: Jean Gauthier-Lafaye, Robert Perron
  • Patent number: 4430506
    Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) vanadium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.
    Type: Grant
    Filed: July 6, 1981
    Date of Patent: February 7, 1984
    Assignee: Rhone-Poulenc Industries
    Inventors: Jean Gauthier-Lafaye, Robert Perron
  • Patent number: 4425360
    Abstract: The present invention provides pyruvic acid oximes of the general formula: ##STR1## wherein R is a hydrogen atom, a C.sub.3 -C.sub.8 cycloalkyl, C.sub.1 -C.sub.6 alkoxy, cinnamyloxy, phenylamino, phenyl-N-alkylamino or phenylthio radical or an aryl or aryloxy radical, the aryl moiety of which can be substituted one or more times by C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, halogen, hydroxyl, trifluoromethyl, amino, acetylamino, nitrile, nitro or methylenedioxy, A is a straight-chained or branched, saturated or unsaturated aliphatic hydrocarbon chain containing up to 10 carbon atoms, which can be substituted one or more times by halogen or hydroxyl, and R.sub.1 is a C.sub.1 -C.sub.8 alkyl radical, which can be substituted one or more times by halogen, hydroxyl, nitrile, phenyl or carboxyl, or is a nitrile or formyl group, with the proviso that when R--A-- is a methyl or ethyl radical, R.sub.1 is not a methyl radical or a nitrile group and when R--A-- is a benzyl radical, R.sub.
    Type: Grant
    Filed: September 8, 1981
    Date of Patent: January 10, 1984
    Assignee: Boehringer Mannheim GmbH
    Inventors: Hans P. Wolff, Ruth Heerdt, Manfred Hubner, deceased, Hans Kuhnle, Felix H. Schmidt
  • Patent number: 4424166
    Abstract: In the preparation of a 1,1-dihalogenoalkene of the formula ##STR1## in which R.sup.1 is a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain, andX.sup.1 and X.sup.2 each independently is a halogen atom,wherein a carbonyl compound of the formula ##STR2## is reacted with a trihalogenoacetate of the formula ##STR3## in which X.sup.3 is a halogen atom, andM.sup..sym. is an alkali metal ion or one equivalent of an alkaline earth metal ion,in the presence of an approximately equimolar amount of a phosphorus-containing compound, the improvement which comprises employing as said phosphorus-containing compound a phosphorous acid trialkyl ester or a phosphorous acid triamide and effecting the reaction at a temperature between about 0.
    Type: Grant
    Filed: February 23, 1981
    Date of Patent: January 3, 1984
    Assignee: Bayer Aktiengesellschaft
    Inventors: Fritz Maurer, Uwe Priesnitz, Hans-Jochem Riebel
  • Patent number: 4423243
    Abstract: A process for the production of 2,2-dimethyl-3-vinyl-cyclopropanecarboxylic acid derivative of the formula ##STR1## in which R.sup.1 is a hydrogen atom, an alkyl group or a radical of an alcohol which can be used in pyrethroids, andX.sup.1 and X.sup.2 each independently is a halogen atomor a fluorine-substituted alkyl radical, comprising adding (a) a polyhalogenoalkene of the formula ##STR2## in which X.sup.3 and X.sup.4 each independently is a halogen atom, to 1-chloro-3,3-dimethyl-pent-4-en-2-one of the formula ##STR3## in the presence of a catalyst which yields free radicals, or in the presence of a metal salt of the VIII main group or of the sub-group IVa, VIIa or Ib of the periodic system, thereby to obtain a mixture of compounds of the formula ##STR4## and (b) reacting either or both of such compounds with a base of a formula(R.sup.1 --O.sup..crclbar.).sub.n M.sup.n+in whichM is an alkali metal or alkaline earth metal, andn is 1 or 2.
    Type: Grant
    Filed: December 16, 1981
    Date of Patent: December 27, 1983
    Assignee: Bayer Aktiengesellschaft
    Inventors: Manfred Jautelat, Dieter Arlt
  • Patent number: 4419524
    Abstract: The invention relates to a new process for the preparation of cyclopropanecarboxylic acids of the formula (I) ##STR1## wherein X and Y independently stand for halogen, by the alkaline hydrolysis of the corresponding alkyl esters having 1 to 6 carbon atoms in the alkyl moiety, in or without a water-miscible organic solvent, in the presence of a phase transfer catalyst. The hydrolysis is carried out with a 2 to 50% by weight aqueous alkali hydroxide solution. If desired, under suitable conditions the cis/trans ratio of the original ester can be altered in the end products. The cyclopropanecarboxylic acids of the formula (I) are obtained in a high purity and are useful intermediates of insecticidally active pyrethroids.
    Type: Grant
    Filed: February 19, 1982
    Date of Patent: December 6, 1983
    Assignee: Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt
    Inventors: Ferenc Lindwurm, Jozsef Muskovits, Sandor Zoltan, Rezso Kolta, Rudolf Soos, Tivadar Puskas, Eva Somfai, Gyorgy Hidasi
  • Patent number: 4412069
    Abstract: A novel process for the preparation of a compound of the formula ##STR1## wherein X is selected from the group consisting of oxygen and sulfur and n is 1,2 or 3 comprising reacting in an organic solvent in the presence of a strong base the lactone of cis 2,2-dimethyl-3S-(dihydroxymethyl)-cyclopropane-1R-carboxylic acid with a compound of the formula ##STR2## to obtain a compound of the formula ##STR3## reacting the latter with an acid agent in an apolar organic solvent to obtain a compound of the formula ##STR4## and reacting the latter with a basic agent in an apolar organic solvent to obtain a compound of formula I useful for the preparation of insecticidal esters and the novel compounds of formula I wherein n is 1 or 3.
    Type: Grant
    Filed: July 17, 1979
    Date of Patent: October 25, 1983
    Assignee: Roussel Uclaf
    Inventors: Jacques Martel, Jean Tessier, Jean-Pierre Demoute
  • Patent number: 4409398
    Abstract: (1R,cis)-Oxyimino-substituted cyclopropanecarboxylic acids are prepared via a (1R,4R,5S)-4-acetoxy-6,6-dimethyl-2-oxo-3-oxabicyclo [3.1.0]hexane intermediate.
    Type: Grant
    Filed: August 13, 1981
    Date of Patent: October 11, 1983
    Assignee: Shell Oil Company
    Inventor: Steven A. Roman
  • Patent number: 4401601
    Abstract: A process for the preparation of tetrasubstituted cyclopropane compounds of the formula ##STR1## wherein Y is selected from the group consisting of --CN and --COOR, R is selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are individually selected from alkyl of 1 to 4 carbon atoms or R.sub.1 and R.sub.2 or R.sub.3 and R.sub.4 together with the carbon atoms to which they are attached form a carbon homocycle of 3 to 6 carbon atoms with the 2 substituents not forming the ring being alkyl of 1 to 4 carbon atoms or R.sub.1 and R.sub.2 on the one hand and R.sub.3 and R.sub.4 on the other together with the carbon atom to which they are attached form a carbon homocycle of 3 to 6 carbon atoms which are useful intermediates for the preparation of insecticidal esters and novel intermediates.
    Type: Grant
    Filed: March 23, 1981
    Date of Patent: August 30, 1983
    Assignee: Roussel Uclaf
    Inventors: Jacques Martel, Jean Tessier, Jean-Pierre Demoute
  • Patent number: 4390724
    Abstract: Novel 3-formyl-4-methyl-pentanoic acid derivatives of the formula ##STR1## wherein Y is an aromatic group, R.sub.2 and R.sub.3 are individually alkyl of 1 to 4 carbon atoms or taken together with the carbon atom to which they are attached form a carbon homocycle of 3 to 6 carbon atoms, the Rs are alkyl of 1 to 6 carbon atoms or together form a polymethylene of 2 to 3 carbon atoms and Z' is selected from the group consisting of --COOH and Z and Z is selected from the group consisting of cyano and --COOR.sub.1 wherein R.sub.1 is alkyl of 1 to 6 carbon atoms and their preparation which are useful for the preparation of 3-formyl-4-R.sub.2 R.sub.3 -but-3-ene-1-oic acid which is an intermediate for the preparation of a compound of the formula ##STR2## wherein R.sub.4 is hydrogen or the remainder of an alcohol of the formula R.sub.1 OH by the process of copending, commonly assigned U.S. patent application Ser. No. 153,338 filed May 27, 1980.
    Type: Grant
    Filed: April 16, 1982
    Date of Patent: June 28, 1983
    Assignee: Roussel Uclaf
    Inventors: Jacques Martel, Jean Tessier, Jean-Pierre Demoute
  • Patent number: 4390719
    Abstract: 1-Methyl-2-chlorocyclopropanecarboxylic acid and its lower esters are produced by the selective hydrogenating dechlorination of the corresponding 1-methyl-2,2-dichlorocyclopropane compounds. The new materials can be used as intermediate products for the production of pesticides and medicines.
    Type: Grant
    Filed: July 6, 1981
    Date of Patent: June 28, 1983
    Assignee: Degussa Aktiengesellschaft
    Inventors: Werner Schwarze, Axel Kleemann, Wolfgang Leuchtenberger
  • Patent number: 4387104
    Abstract: A pyruvic acid hydrazone derivative of the formula: ##STR1## wherein R is an aryl radical optionally substituted by lower alkyl or is an aliphatic hydrocarbon radical which can be substituted by a lower alkoxy, a cycloalkyl or an optionally substituted aryl radical,A is an alkylene radical containing 2 to 8 carbon atoms, with at least 2 carbon atoms between B and the nitrogen atom, andB is an oxygen or sulphur atom;or a physiologically acceptable salt, ester or amide thereof which possesses hypoglycaemic activity.
    Type: Grant
    Filed: August 14, 1981
    Date of Patent: June 7, 1983
    Assignee: Boehringer Mannheim GmbH
    Inventors: Ruth Heerdt, Hans P. Wolff, Fritz Kaiser, Wolfgang Schaumann, Hans Kuhnle
  • Patent number: 4386103
    Abstract: Dichloroamino acid derivatives other than .alpha.-dichloroamino acids are prepared from chlorination of corresponding amino acids, and are found to be potent germicidal and fungicidal agents.
    Type: Grant
    Filed: January 30, 1981
    Date of Patent: May 31, 1983
    Assignee: Merck & Co., Inc.
    Inventors: Stefano A. Pogany, Takeru Higuchi
  • Patent number: 4375557
    Abstract: Novel compounds of the formula I ##STR1## in which each of Y.sup.1 and Y.sup.2 independently represents a fluorine, chlorine or bromine atom and each of R.sup.1 and R.sup.2 independently represents a hydrogen atom or an alkyl group having up to 10 carbon atoms, or R.sup.1 and R.sup.2 together represent an alkylene group having from 2 to 5 carbon atoms, may be converted by the action of base into the corresponding dihalovinylcyclopropane carboxylic acids.
    Type: Grant
    Filed: June 7, 1982
    Date of Patent: March 1, 1983
    Assignee: Shell Oil Company
    Inventor: Petrus A. Kramer
  • Patent number: 4367344
    Abstract: A process for the preparation of 1-amino-cyclopropane-carboxylic acid or a derivative thereof of the general formula ##STR1## in which R.sup.1 represents hydrogen or alkyl andR.sup.2 represents hydrogen or a radical --CO--R.sup.3, whereinR.sup.3 represents hydrogen, alkyl, aryl or alkoxy, in which a 2-cycloamino-4-methylthio-butanoic acid ester ("acyl-methionine ester") of the general formula ##STR2## in which R.sup.3 has the meaning indicated above andR.sup.4 represents alkyl,is reacted successively with dimethyl sulphate and an alkali metal alcoholate, if appropriate in the presence of a diluent, at a temperature between 80.degree. C. and 150.degree. C., the product is then optionally saponified with aqueous alkali metal hydroxide or alkaline-earth metal hydroxide at a temperature between 70.degree. C. and 150.degree. C., the reaction mixture thereby obtained is acidified with concentrated hydrochloric acid at a temperature between 0.degree. C. and 30.degree. C.
    Type: Grant
    Filed: August 22, 1980
    Date of Patent: January 4, 1983
    Assignee: Bayer Aktiengesellschaft
    Inventor: Bernd Gallenkamp
  • Patent number: 4363926
    Abstract: A bissilylated 1-hydroxycyclopropanecarboxylic acid of the formula ##STR1## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each independently is a hydrogen atom or an alkyl radical, and additionally R.sup.2 and R.sup.3 can together form a 3- to 5-membered carbon bridge, andR.sup.5, R.sup.6 and R.sup.7 each independently is an alkyl radical, is produced by oxidizing with oxygen a cyclobutene-1,2-diol-bis-trialkyl-silyl ether of the formula ##STR2## The products, without isolation, may directly be hydrolyzed to remove the silyl radicals and form known intermediates for further reaction.
    Type: Grant
    Filed: September 18, 1981
    Date of Patent: December 14, 1982
    Assignee: Bayer Aktiengesellschaft
    Inventors: Hans-Georg Heine, Hans-Joachim Knops, Uwe Priesnitz
  • Patent number: 4350824
    Abstract: A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or the two radicals R.sup.3 together are alkanediyl,in the presence of at least an equimolar amount of a phosphorous acid triamide of the formulaP(NR.sup.4.sub.2).sub.3in whichR.sup.4 each independently is an alkyl radical, or the two radicals R.sup.4 together are alkanediyl.Advantageously,R.sup.1 is hydrogen,R.sup.2 a C.sub.2 to C.sub.
    Type: Grant
    Filed: February 23, 1981
    Date of Patent: September 21, 1982
    Assignee: Bayer Aktiengesellschaft
    Inventors: Hans-Jochem Riebel, Fritz Maurer, Uwe Priesnitz
  • Patent number: 4346038
    Abstract: Novel compounds of the formula I ##STR1## in which each of Y.sup.1 and Y.sup.2 independently represents a fluorine, chlorine or bromine atom and each of R.sup.1 and R.sup.2 independently represents a hydrogen atom or an alkyl group having up to 10 carbon atoms, or R.sup.1 and R.sup.2 together represent an alkylene group having from 2 to 5 carbon atoms, may be converted by the action of base into the corresponding dihalovinylcyclopropane carboxylic acids which are intermediates for preparing known pyrethroid insecticides.
    Type: Grant
    Filed: September 28, 1981
    Date of Patent: August 24, 1982
    Assignee: Shell Oil Company
    Inventor: Petrus A. Kramer
  • Patent number: 4344884
    Abstract: Novel intermediates for production of insecticidal cis-3-(2,2-disubstituted-ethenyl)-2,2-dimethylcyclopropanecarboxylates, processes for preparing the intermediates, and processes for preparing the final product insecticides via a novel bicyclic lactone intermediate are described and exemplified.
    Type: Grant
    Filed: June 30, 1980
    Date of Patent: August 17, 1982
    Assignee: FMC Corporation
    Inventors: Kiyoshi Kondo, Toshiyuki Takashima, Minoru Suda
  • Patent number: 4342704
    Abstract: A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aralkenyl or aryl radical, or cycloalkyl which is optionally substituted by halogen, alkyl, alkanoyl, carbamoyl, cyano or phenyl, orR.sup.1 and R.sup.2 together form a hydrocarbon chain which is optionally branched and/or optionally contains a fused benzene ring,comprising reacting an aldehyde or ketone of the formula ##STR2## with a dichloromethane-phosphonic acid ester of the formula ##STR3## in which R.sup.3 each independently is alkyl or phenyl or the two radicals R.sup.3 together are alkanediyl,in the presence of a base at a temperature between about -50.degree. and +50.degree. C.
    Type: Grant
    Filed: July 2, 1980
    Date of Patent: August 3, 1982
    Assignee: Bayer Aktiengesellschaft
    Inventors: Hellmut Hoffmann, Fritz Maurer, Uwe Priesnitz, Hans-Jochem Riebel