Mitsui Petrochemical Industries, Ltd.

Sumitomo Chemical Company, Limited

Mitsui Chemicals, Inc.

Teruaki Mukaiyama

Yoji Sakito

Masatoshi Asami

Junichi Imuta

Noriaki Kihara

Toru Yamada

Takashi Ueda

Junji Saito

Isao Hashimoto

Masahiro Usui

Katsuya Takahashi

Kiyoaki Sugi

Takeshi Ishitoku

Kunihiro Oouchi

Makoto Mitani

Kazuhiko Saigo

Takushi Nagata

Daisuke Fukuoka

Takashi Tashiro

Ikuo Tomino

Hiroshi Iwasaki

Hiroaki Tan

Hiroyasu Ohno

Shintaro Araki

Masaharu Ishiguro

Kiyotaka Yorozu

Eiichiro Shimada

Houji Kato

A novel process for producing an optically active amine is provided. The optically active amine is adapted for use as an intermediate in synthesizing physiologically active compounds such as pharmaceuticals and agricultural chemicals, as a functional material such as a liquid crystal, and as a starting material in synthesizing fine chemicals. The process comprises the step of reacting an imine with a hydride reagent in the presence of an optically active metal compound and an alcohol compound and/or carboxylic acid compound.

Process for producing optically active amine

Disclosed in an olefin polymerization catalyst comprising a transition metal compound having at least two transition metals in which at least one of said metals is bonded to a ligand having a cyclopentadienyl skeleton, at least one of said metals is selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals and at least on of the others is selected from the specific transition metals; and an organoaluminum oxy-compound or an organoboron compound. Corresponding to the kind of the metal combined with said metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, the olefin polymerization catalyst exhibit a property to give polymers having a wide molecular weight distribution in spite of the catalyst system using one kind of a transition metal compound, or to give polymers having high molecular weight and be excellent in the polymerization activity at low polymerization temperature.

Olefin polymerization catalyst and process for olefin polymerization

The invention provides a method for preparing an optically active alcohol comprising the step of reacting a ketone compound with a hydride reagent in the presence of an optically active metal compound. The resulting optically active alcohols are useful as intermediates for the synthesis of physiologically active compounds such as drugs and pesticides, functional materials such as liquid crystals, and raw materials for synthesis in fine chemistry. A novel optically active cobalt (II) complex useful as a catalyst is also provided.

Optically active cobalt (II) complexes and method for the preparation of

Process for producing aromatic hydroxylic compound

The catalyst for olefin polymerization of the present invention contains R.sub.k.sup.1 R.sub.l.sup.2 R.sub.m.sup.3 M(SO.sub.3 R.sup.4) (M=Zr, Ti or Hf; R.sup.1-3 =a group having a cyclopentadienyl skeleton) as a catalyst component of a transition metal compound. According to the catalyst of the invention, an olefin polymer having excellent particle properties can be prepared with high polymerization activities, and further a copolymer having a narrow composition distribution can be prepared when two or more monomers are copolymerized. Of the above-mentioned transition metal compounds, a compound represented by the following formula is a novel compound unknown so far and shows excellent catalytic properties. ##STR1## (Cp=a group having a cyclopentadienyl skeleton, X=SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P (O).sub.q R.sub.3, n=1, 2 or 3; q=0, 1 or 2)

Catalyst for olefin polymerization, process for the polymerization of

The catalyst for olefin polymerization of the present invention contains R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m M(SO.sub.3 R.sup.4) (M=Zr, Ti or Hf; R.sup.1-3 =a group having a cyclopentadienyl skeleton) as a catalyst component of a transition metal compound. According to the catalyst of the invention, an olefin polymer having excellent particle properties can be prepared with high polymerization activities, and further a copolymer having a narrow composition distribution can be prepared when two or more monomers are copolymerized. Of the above-mentioned transition metal compounds, a compound represented by the following formula is a novel compound unknown so far and shows excellent catalytic properties. ##STR1## (Cp=a group having a cyclopentadienyl skeleton, X=SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P(O).sub.q R.sub.3, n=1, 2 or 3; q=0, 1 or 2)

Process for preparing polyalkyl-2-alkoxy-7-hydroxychroman derivative of the general formula (V): ##STR1## wherein R.sup.1 denotes lower primary alkyl, R.sup.2 denotes hydrogen or lower primary alkyl and R.sup.3 denotes loweralkyl, by reacting resorcin with either an aliphatic ketone of the general formula (I): ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, and an alcohol of the formula (II):

Process for preparing polyalkyl-2-alkoxy-7-hydroxychroman derivatives

A novel cyanoguanidine derivative represented by the following general formula (I): ##STR1## wherein X stands for a hydrogen atom, a chlorine atom or a bromine atom, and R stands for a lower alkyl group, is an effective precursor for the synthesis of N-cyano-N'-methyl-N'-(2-(5-methyl-4-imidazolylmethylthio(ethyl)-guanidine (Cimetidine) which has an action of controlling secretion of gastric acid and is valuable as an agent for the remedy of a gastric ulcer. This cyanoguanidine derivative is prepared by reacting a methylvinylketone derivative with a mercaptoguanidine derivative or by reacting an amidinoketone derivative with a halogenating agent.

Cyanoguanidine derivative and process for preparation thereof

N-cyano-N'-methyl-N'-(2-(5-methyl-4-imidazolylmethylthio)ethyl)guanidine (Cimetidine), which is valuable as an agent for controlling secretion of gastric acid, is prepared in a high yield by reacting N-cyano-N'-methyl-N'-(2-(butane-2,3-dionyl)thioethyl)-guanidine as the starting compound with an ammonium salt of a carboxylic acid and formaldehyde.

Process for preparation of guanidine derivative

An optically active or inactive .beta.-formyl-.beta.-hydroxy ester of the formula (1), ##STR1## wherein R.sup.1 represents a C.sub.1 -C.sub.10 alkyl, C.sub.3 -C.sub.10 alkenyl, C.sub.2 -C.sub.10 alkynyl, C.sub.6 -C.sub.14 aryl or C.sub.7 -C.sub.14 aralkyl group, R.sup.2 represents a C.sub.1 -C.sub.4 alkyl group and R.sup.3 represents a hydrogen atom or a C.sub.1 -C.sub.10 alkyl group, and a method for producing the same which comprises reacting an optically active or inactive compound of the formula (2), ##STR2## wherein A represents a C.sub.6 -C.sub.14 aryl group and R.sup.1 is as defined above, with an .alpha.-halo ester of the formula (3), ##STR3## wherein X represents a halogen atom and R.sup.2 and R.sup.3 are as defined above, in the presence of zinc, followed by hydrolysis, or reacting an ester of the formula (4),

.beta.-formyl-.beta.-hydroxy ester

An optically active or racemic .alpha.-hydroxyaldehyde represented by the general formula (2), ##STR1## wherein R.sub.1 represents a C.sub.6 -C.sub.14 aryl group, C.sub.1 -C.sub.10 alkyl group, C.sub.3 -C.sub.10 alkenyl group, C.sub.2 -C.sub.10 alkynyl group, C.sub.7 -C.sub.14 aralkyl group, or a group containing a functional group in the organic portion of said groups and R.sub.2 represents a C.sub.1 -C.sub.10 alkyl group, C.sub.2 -C.sub.10 alkenyl group, C.sub.2 -C.sub.10 alkynyl group, C.sub.7 -C.sub.14 aralkyl group, C.sub.6 -C.sub.14 aryl group, or a group containing a functional group in the organic portion of these groups, which is an important intermediate for preparation of pharmaceuticals and agricultural chemicals, and prepared by allowing an optically active or racemic compound represented by the general formula (1), ##STR2## (wherein A represents a C.sub.6 -C.sub.14 aryl group or a C.sub.1 -C.sub.4 alkyl or alkoxy group- or halogen-substituted C.sub.6 -C.sub.14 aryl group and R.sub.1 is as defined above) to react with a Grignard reagent, and thereafter hydrolyzing the reaction product.

Acyl and ester derivatives of 1,3-diazabicyclo[3,3,0]octane

Process for preparing .alpha.-hydroxyaldehyde

An optically active or racemic .alpha.-hydroxyaldehyde represented by the general formula (2), ##STR1## wherein R.sub.1 represents a C.sub.6 -C.sub.14 aryl group, C.sub.1 -C.sub.10 alkyl group, C.sub.3 -C.sub.10 alkenyl group, C.sub.2 -C.sub.10 alkynyl group, C.sub.7 -C.sub.14 aralkyl group, or a group containing a functional group in the organic portion of said groups and R.sub.2 represents a C.sub.1 -C.sub.10 alkyl group, C.sub.2 -C.sub.10 alkenyl group, C.sub.2 -C.sub.10 alkynyl group, C.sub.7-C.sub.14 aralkyl group, C.sub.6 -C.sub.14 aryl group, or a group containing a functional group in the organic portion of these groups, which is an important intermediate for preparation of pharmaceuticals and agricultural chemicals, and prepared by allowing an optically active or racemic compound represented by the general formula (1), ##STR2## (wherein A represents a C.sub.6 -C.sub.14 aryl group or a C.sub.1 -C.sub.4 alkyl or alkoxy group- or halogen-substituted C.sub.6 -C.sub.14 aryl group and R.sub.1 is as defined above) to react with a Grignard reagent, and thereafter hydrolyzing the reaction product.

.alpha.-Hydroxyaldehyde and a process for preparing the same

A method for producing optically active or racemic 1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane characterized by reducing optically active or racemic 2-hydroxy-2,6-dimethyl-6-heptenal and oxidizing the resuling optically active or racemic 2,6-dimethyl-6-heptene-1,2-diol, and optically active or racemic 2,6-dimethyl-6-heptene-1,2-diol.

Growing community of inventors

Tokyo, Japan

Teruaki Mukaiyama