Kuraray Co., Ltd.

Sagami Chemical Research Center

Taiho Pharmaceutical Company Limited

Fumio Mori

Takashi Nishida

Yoshiaki Omura

Kazuo Itoi

Yoshiji Fujita

Takeo Hosogai

Yoshin Tamai

Fumio Wada

Sukeji Aihara

Yoichi Ninagawa

Takashi Ohnishi

Kiyosi Kondo

Iwao Ebashi

Masafumi Okada

Masahisa Tanomura

Shigeru Tsukagoshi

Tazuko Tashiro

Kouichiro Kawai

Shuji Miki

Shigeaki Suzuki

Manzo Shiono

Takashi Onishi

Norio Unemi

Setsuo Takeda

Masakatsu Matsumoto

Tetsuo Takigawa

Masao Tsuji

Masao Mizuno

Hitoshi Saito

Yoshihiro Ichihara

Tsutomu Kawai

A pullulan derivative having one or more active sites resulting from introduction of sulfuric acid, phosphoric acid, a sulfonic acid or a carboxylic acid, wherein one hydrogen atom of the group of the formula ##STR1## occurring at said active sites is partly substituted by a group of the general formula ##STR2## wherein L.sup.1 and L.sup.2 each independently is amine or a unidentate ligand amine or combinedly represent a bidentate ligand amine and Y is an anionic ligand, and/or two hydrogen atoms of the group ##STR3## groups bound to one and the same carbon atom or to two neighboring carbon atoms as occurring at said active sites are, each independently, partly substituted by a group of the general formula ##STR4## wherein L.sup.1 and L.sup.2 are as defined above, and a pharmacologically acceptable salt thereof. The above compound has anticancer activity and is useful as anticancer agents. The present invention is concerned with said compound, a process for producing the same and a pharmaceutical use thereof.

Platinum containing pullulan derivatives and pharmaceutical compositions

2'-Deoxy-5-fluorouridine derivatives of the formula ##STR1## wherein, R.sup.1 is hydrogen atom or an acyl group and R.sup.2 and R.sup.3 are respectively hydrogen atom, an acyl group or a group of the formula ##STR2## wherein X.sup.1 and X.sup.2 are respectively oxygen atom or sulfur atom; R.sup.4 is a phenyl group, a benzyl group or a naphthyl group each of which may be substituted by an alkyl group, an alkoxyl group, an alkoxycarbonyl group, an alkylthio group, and acyl group, a halogen atom, trifluoromethyl group, nitro group, cyano group, carboxyl group and/or methylenedioxy group and R.sup.5 is an alkyl group, an alkenyl group or one of the groups represented by R.sup.4 which is the same as or different from R.sup.4, at least one of R.sup.2 and R.sup.3 being a group of the formula ##STR3## which exhibit excellent antitumour activities and have lower toxicity, methods of the production thereof and antitumour compositions containing said 2'-deoxy-5-fluorouridine derivatives.

2'-deoxy-5-fluorouridine derivatives

Platinum containing pullulan derivatives and compositions containing the

Novel polyprenyl compounds have the general formula: ##STR1## represents a cis-isoprene unit, n is an integer of 11-19, Z.sup.1 is --CH.sub.2 OH or a functional precursor thereof, and either one of R.sup.1 and R.sup.2 is a hydrogen atom and the other is --S(O).sub.m R.sup.3 in which m is an integer of 0 (zero), 1 or 2 and R.sup.3 is a phenyl, naphthyl, pyridyl or thiazolinyl group or such group substituted with at least one lower alkyl and/or halogen substituent. The topic novel polyprenyl compounds can be synthesized from derivatives of the polyprenol which is obtainable from leaves of Ginkgo biloba or Cedrus deodara, among others, by extraction, if necessary followed by hydrolytic treatment. The novel polyprenyl compounds can be converted to mammalian dolichols or precursors thereof by reductive elimination of the --S(O).sub.m R.sup.3 group.

Certain polyprenyl intermediates

There is provided the novel compound 11-hydroxypregn-4-en-3-one-20-carbaldehyde, as well as a microbial method for production of the same. This novel compound is of value as a starting material for antiinflammatory corticoids such as hydrocortisone, cortisone, prednisolone and prednisone.

11-hydroxypregn-4-en-3-one-20-carbaldehyde and a method for its

Novel pesticidal compositions are comprised of a 2,2-dimethyl-3-(substituted ethyl)cyclopropanecarboxylic acid ester as the active ingredient, said cyclopropanecarboxylate having the structural formula: ##STR1## wherein X, Y and Z are the same or different and at least two of same are chlorine or bromine, with the remaining one being hydrogen, methyl, chlorine or bromine; R is an alcohol residue represented by one of the following structural formulae (II), (III), (IV) and (V): ##STR2## where A represents hydrogen, cyano, ethynyl or thiocarbamoyl; Q is hydrogen, chlorine, bromine, fluorine, methyl or trifluoromethyl; R.sup.1 is propargyl or benzyl; R.sup.2 represents 2-halogeno-3-phenyl-1-propen-1-yl, (dihalogenovinyloxy)phenyl, benzylphenyl, phthalimido, thiophthalimido, di- or tetrahydrophthalimido or dialkylmaleimido; R.sup.3 represents allyl, 2,4-pentadienyl, propargyl or benzyl.

Certain cyclopropane carboxylic acid esters and their pesticidal use

Novel insecticidal compositions are comprised of an active isovalerate having the structural formula: ##STR1## wherein Z.sup.1 is hydrogen, ##STR2## Z.sup.2 is either ##STR3## when Z.sup.1 is hydrogen, or hydrogen when Z.sup.1 is either ##STR4## A, when Z.sup.1 is ##STR5## is cyano or ethynyl or, when Z.sup.1 is other than ##STR6## is hydrogen, cyano or ethynyl; X and Y which may be the same or different are chlorine or bromine.

Insecticides and insecticidal compositions

2,2-Dimethyl-3-(substituted ethyl)cyclopropane carboxylate pesticidal

A new pyrethroid compound which is low in toxicity to fish and a pesticidal composition containing the same as an active ingredient are provided. The above pyrethroid compound is a substituted cyclopropanecarboxylic acid ester of the general formula: ##STR1## (wherein A is a hydrogen atom or an ethynyl group) Despite its broad pesticidal spectrum and high pesticidal activity, this ester is very low in toxicity to man and domestic animals and especially low in toxicity to fish as compared with the conventional pyrethroid compounds.

Substituted cyclopropanecarboxylic acid esters and pesticidal

Racemic modifications each consisting of specific isomers of .alpha.-cyano-3-phenoxybenzyl cis- or trans-2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate with the absolute configurations [.alpha.S, 1R] an [.alpha.R, 1S] with respect to the asymmetric carbon atoms in the alcohol and acid moieties, a method of producing the same and pesticidal compositions containing the same as active ingredient are provided. .alpha.-Cyano-3-phenoxybenzyl cis- or trans-2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate has higher pesticidal activities than those pesticides that are in general use and consequently selective production of the above specific racemic modification as defined by the combinations of the absolute configuration with respect to the asymmetric carbon atom at the position in the alcohol moiety and the absolute configuration with respect to the asymmetric carbon atom in the acid moiety provides compounds having still higher pesticidal activities.

Racemic modification consisting of specific isomers of

Novel pesticidal compositions are comprised of a 2,2-dimethyl-3-(substituted ethyl)cyclopropanecarboxylic acid ester as the active ingredient, said cyclopropanecarboxylate having the structural formula: ##STR1## wherein X, Y and Z are the same or different and at least two of same are chlorine or bromine, with the remaining one being hyrogen, methyl, chlorine or bromine; R is an alcohol residue represented by one of the following structural formulae (II), (III), (IV) and (V): ##STR2## where A represents hydrogen, cyano, ethynyl or thiocarbamoyl; Q is hydrogen, chlorine, bromine, fluorine, methyl or trifluoromethyl; R.sup.1 is propargyl or benzyl; R.sup.2 represents 2-halogeno-3-phenyl-1-propen-1-yl, (dihalogenovinyloxy)phenyl, benzylphenyl, phthalimido, thiophthalimido, di- or tetrahydrophthalimido or dialkylmaleido; R.sup.3 represents allyl, 2,4-pentadienyl, propargyl or benzyl.

Novel pesticides and pesticidal compositions cyclopropanecarboxylates

Novel substituted propargyl alcohols of the formula: ##STR1## novel allylic alcohols of the formula: ##STR2## and; .delta.,.epsilon.-unsaturated ketones of the formula: ##STR3## are provided. In the above formulas, R represents a group of the formula: ##STR4## wherein X.sub.1 and X.sub.2 are both hydrogen atoms or wherein one of X.sub.1 and X.sub.2 is a hydrogen atom, the other jointly with Z represents a bond; Z jointly with X.sub.1 or X.sub.2 represents a bond or separately represent a hydrogen atom, a hydroxyl group or a lower alkoxy group; R.sub.1 and R.sub.2 are the same or different and represents hydrogen atoms or lower alkyl groups; n is 1 or 2; and when n is 2, X.sub.1, X.sub.2, X, R.sub.1 and R.sub.2 may be the same or different. These novel compounds are easily produced and are useful as perfumes and as interrelated intermediates for the production of terpenoid compounds.

Substituted propargyl alcohols, allylic alcohols and unsaturated

A 1,1,1-trihalogeno-4-methyl-3-penten-2-ol is prepared by thermally isomerizing 1,1,1-trihalogeno-4-methyl-4-penten-2-ol. The isomerization reaction may be catalyzed by an acid or a transition metal of Group 6B, 7B or 8 of the Periodic Table of Elements, or a compound thereof. The 1,1,1-trihalogeno-4-methyl-3-penten-2-ol thus prepared is useful as a synergist for herbicides or a physiologically active compound, and, additionally, is useful as a starting material for the synthesis of 2,2-dimethyl-3-(2',2'-dihalogenovinyl)-cyclopropane carboxylic esters which are active ingredients of insecticides.

Preparation of 1,1,1-trihalogeno-4-methyl-3-penten-2-ol

Novel substituted propargyl alcohols of the formula: ##STR1## novel allylic alcohols of the formula: ##STR2## .delta.,.epsilon.-unsaturated ketones of the formula: ##STR3## are provided. In the above formulas, R represents a group of the formula: ##STR4## wherein X.sub.1 and X.sub.2 are both hydrogen atoms or wherein one of X.sub.1 and X.sub.2 is a hydrogen atom, the other jointly with Z represents a bond; Z jointly with X.sub.1 or X.sub.2 represents a bond or separately represent a hydrogen atom, a hydroxyl group or a lower alkoxy group; R.sub.1 and R.sub.2 are the same or different and represents hydrogen atoms or lower alkyl groups; n is 1 or 2; and when n is 2, X.sub.1, X.sub.2, X, R.sub.1 and R.sub.2 may be the same or different. These novel compounds are easily produced and are useful as perfumes and as interrelated intermediates for the production of terpenoid compounds.

There is disclosed a process for preparing unsaturated ketones especially terpenoid ketones, by subjecting a substituted propargyl alcohol of formula (II) ##STR1## wherein R is a group containing 1 or 2 substituted or unsubstituted alkyl- or alkylene units containing 4 carbon atoms each to a thermal treatment sufficient to rearrange its structure in order to obtain structurally isomeric unsaturated ketones of formula I ##STR2## wherein one of the substituents X.sub.3 and X.sub.4 is hydrogen and the other and Z.sub.2 together form a bond. The process can be effected in the presence of an isomerization catalyst, which leads to high percentage of .alpha...beta.,.gamma...delta.-unsaturated ketones. The ketones of formula I are useful as perfumes and as intermediates for the production of terpenoid compounds.

Growing community of inventors

Kurashiki, Japan

Fumio Mori