公开(公告)号：JPH0640974A

公开(公告)日：1994-02-15

申请号：JP21956792

申请日：1992-07-28

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: B01J31/02 ,  C07C31/38 ,  C07C31/44 ,  C07C33/42 ,  C07C33/44 ,  C07C33/46 ,  C07C41/26 ,  C07C43/225 ,  C07F7/18

Abstract: PURPOSE:To provide a process for producing an alcohol derivative having difluoromethyl group at alpha-site and important as a raw material for pharmaceuticals, agricultural chemicals, functional materials, etc. CONSTITUTION:The alcohol derivative having difluoromethyl group at alpha-site and expressed by the general formula R R C(OSiR R R )-CF2H or R R C(OH)-CF2 H [R and R are independently H or (substituted) alkyl, aromatic group, aralkyl, alkenyl or alkynyl; R and R may together form a ring; R , R and R are independently alkyl or aromatic group) is produced by reacting a carbonyl compound expressed by the general formula R R C=O with a difluoromethylsilane expressed by the general formula R R R Si-CF2H in the presence of an alkoxide ion source.

公开(公告)号：JPH05230075A

公开(公告)日：1993-09-07

申请号：JP6975492

申请日：1992-02-19

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: C07F7/18 ,  C07C29/38 ,  C07C33/18

Abstract: PURPOSE:To produce an alcohol derivative important as a raw material for medicines, agricultural agent, functional material, etc., and having a difluoromethyl group at a position. CONSTITUTION:The objective alcohol derivative expressed by the formula R R C (OSiR R R )-CF2H or the formula R R C(OH)-CF2H (R and R are each independently hydrogen atom or alkyl group, aromatic group, aralkyl group, alkenyl group or alkynyl group which may have substituent or R and R together may form a ring; R , R and R are each independently alkyl group or aromatic group) and having a difluoromethyl group at alpha position is produced by reacting a carbonyl compound expressed by the formula R R C=O with a difluoromethylsilanes of the formula R R R Si-CF2H in the presence of a fluoride ion source. Thereby, the alcohol derivative having difluoromethyl group at alpha-position can simply be synthesized.

公开(公告)号：JPH11158145A

公开(公告)日：1999-06-15

申请号：JP32600797

申请日：1997-11-27

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: C07D209/18 ,  A01N43/38

Abstract: PROBLEM TO BE SOLVED: To simply obtain the subject compound useful as a plant growth promoter in a single step by reacting indoles with a base having a definite strength or above and reacting the resultant compound with a trifluorocrotonic acid derivative. SOLUTION: Indoles of formula I (X is H, a lower alkyl or a halogen) are reacted with (B) a base in which pKa of conjugate acid is larger than pKa of the component A (e.g. an alkyl metal compound such as methyllithium or a metal alkoxide such as sodium ethoxde) and then reacted with (C) 4,4,4- trifluorocrotonic acid derivative of formula II (R is an ester type or amide type protecting group of carboxylic acid part) to provide the objective 4,4,4- trifluoro-3-(3-incolyl)lactic acid (TFIBA) of formula III. Furthermore, the component C is preferably used in 0.7-1 equivalent amount based on the component A. According to this method, TFIBA whose carboxyl group is protected can be obtained in a single step.

公开(公告)号：JPH09295948A

公开(公告)日：1997-11-18

申请号：JP67097

申请日：1997-01-07

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI ,  YAMAMOTO TOSHINORI

IPC: C07D209/48 ,  B01J27/12 ,  B01J27/236 ,  C07B41/12 ,  C07B45/06 ,  C07B47/00 ,  C07B53/00 ,  C07B61/00 ,  C07C67/11 ,  C07C69/78 ,  C07C319/14 ,  C07C323/07 ,  C07F9/6568

Abstract: PROBLEM TO BE SOLVED: To obtain a fluorine-containing compound useful as a synthetic intermediate for a medicine, a chemical or a functional material, by carrying out the functional replacement reaction of an α-perfluoroalkylated alcohol derivative, which has been regarded to be difficult, in the presence of a specific compound. SOLUTION: A sulfonic acid ester of an α-perfluoroalkylated alcohol of formula I (R and R are each H, an alkyl, an aromatic group, an aralkyl, an alkenyl or R and R form a ring with an adjoining carbon atom; Rf is a perfluoroalkyl; R is an alkyl, an aromatic group or a halogen) is reacted with a nucleophilic reagent of the formula HY [Y is Q R , Q R R (Q is O, S, selenium or tellurium; Q is N, P or arsine; R to R are each H, alkyl, an aromatic group, etc.; R and R form a ring) in the presence of a basic substance to give a fluorine-containing compound of formula II. NaOH, KF, phenyllithium may be cited as the basic substance. For example, a compound of formula V is obtained from a compound of formula III and a compound of formula IV by using the method.

公开(公告)号：JPH0881400A

公开(公告)日：1996-03-26

申请号：JP21708294

申请日：1994-09-12

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: C07C29/10 ,  C07C29/14 ,  C07C29/143 ,  C07C31/38 ,  C07C31/44 ,  C07C33/46 ,  C07F7/18

Abstract: PURPOSE: To provide a simple method of giving an alcohol derivative bearing a difluoromethylene group in the α-position, which is important as a starting substance for medicines, agrochemicals or functional materials. CONSTITUTION: A method of producing an alcohol derivative bearing a difluoromethylene group in the α-position, represented by the general formula: R R C(OSiR R R )-CF2 -R or R R C(OH)-CF2 -R (R and R are each H or an alkyl, alkenyl, or alkynyl group, or they may form a ring together with carbon atoms; R , R , R are each an alkyl or an aromatic group; R is an alkyl, aromatic, aralkyl, alkenyl and alkynyl group) comprises the reaction of a carbonyl compound of the general formula: R R C=O with a perfluoroalkylsilane of the general formula: R R R Si-CF2 -R in the presence of a reaction promotor.

公开(公告)号：JPH10330354A

公开(公告)日：1998-12-15

申请号：JP14249797

申请日：1997-05-30

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: G02F1/13 ,  C07C323/03 ,  C07C323/05 ,  C07C323/07 ,  C07C327/02 ,  C07C327/20 ,  C07C327/28 ,  C07C327/32 ,  C07C327/36 ,  C09K19/20

Abstract: PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a synthetic intermediate for a medical or agricultural agent such as an anticancer agent or an enzyme inhibitor, or a functional material such as ferroelectric liquid crystal. SOLUTION: This compound is an optically active α-trifluoromethylated thiol of formula I [R is an alkyl, an aromatic group, an aralkyl, an alkenyl, etc.; R is an acyl of C(=O)R (R is H, an alkyl, etc.), etc.; * is an optically active C-atom] or its ester derivative, e.g. (S)-thioacetic acid S-1-(trifluoromethyl)heptyl ester. A compound of formula I is obtained e.g. by reacting an optically active α-trifluoromethylated alcohol of formula II with trifluoromethanesulfonic anhydride in the presence of a base such as pyridine in a solvent such as ether.

公开(公告)号：JPH10287596A

公开(公告)日：1998-10-27

申请号：JP14249897

申请日：1997-05-30

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: A61K31/40 ,  A61K31/02 ,  A61K31/075 ,  A61K31/215 ,  A61K31/23 ,  A61K31/26 ,  A61K31/403 ,  A61K31/4035 ,  A61P35/00 ,  C07C17/093 ,  C07C19/10 ,  C07C19/14 ,  C07C41/16 ,  C07C43/12 ,  C07C67/11 ,  C07C69/62 ,  C07C247/04 ,  C07C253/30 ,  C07C255/19 ,  C07C327/40 ,  C07C331/04 ,  C07D209/48

Abstract: PROBLEM TO BE SOLVED: To simply obtain a fluorine-containing compound by reacting an α- perfluoroalkylated alcohol with a Broensted acid in an aprotic solvent. SOLUTION: A perfluoroalkylsulfonic acid ester or perfluoroarylsulfonic acid ester of an α-perfluoroalkylated alcohol of the formula R R Rf C-OSO2 Rf [R and R are each H, an alkyl, an aromatic, an aralkyl, an alkenyl or an alkynyl or R and R together may form a ring; Rf and Rf are each a perfluoroalkyl or a perfluoro aromatic] is reacted with a Broensted acid of the formula M m Q n [M is a metal ion or polyatomic cation; Q is a conjugated base of the Broensted acid QHy ; (x), (y), (m) and (n) are each an integer satisfying the formula xm=yn] in a solvent such as DMF at -100 to 200 deg.C to provide the objective fluorine-containing compound of the formula (R R Rf C-)y Q (Q is a Broensted acid residue). The compound can be utilized as a synthetic intermediate for medicines and agrochemicals such as aticancer agents and enzyme inhibitors and functional materials such as ferroelectric liquid crystals.

公开(公告)号：JPH08113580A

公开(公告)日：1996-05-07

申请号：JP25109694

申请日：1994-10-17

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: C07F7/18

Abstract: PURPOSE: To produce an amino alcohol derivative having a fluoroalkyl group and usable as a synthetic intermediate for pharmaceuticals, agrochemicals and functional materials and a building block used for the synthesis of various fluorine-containing compounds. CONSTITUTION: An aminocarbonyl compound expressed by the general formula R C(C=O)-R -NR R is reacted with a fluoroalkylsilane expressed by the general formula R R R Si-CF2 R to obtain a compound expressed by the general formula R C(OSiR R R )-(CF2 -R )-R -NR R , which is hydrolyzed to give a fluoroalcohol derivative expressed by the general formula R C(OH)-(CF2 -R )-R -NR R .

公开(公告)号：JPH07118188A

公开(公告)日：1995-05-09

申请号：JP28213993

申请日：1993-10-18

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: B01J31/02 ,  C07B61/00 ,  C07C29/124 ,  C07C31/40 ,  C07C33/46 ,  C07F7/18

Abstract: PURPOSE:To easily obtain an alcohol derivative having a perfluoroalkyl group at ALPHA-site important as a raw material for medicines, agrochemicals, functional materials, etc. CONSTITUTION:The objective alcohol derivative having perfluoroalkyl group at the alpha-site of general formula R R C(OSiR R R )-CnF2n+1 or R R C(OH)-CnF2n+1 [R and R are each H or (substituted) akyl, aromatic group, aralkyl, alkenyl or alkynyl, or may together be combined into a ring; R , R and R are each alkyl or aromatic group; n is an integer of 1-10] can be obtained by reaction between (A) a carbonyl compound of general formula R R C=O and (B) a silane of general formula R R R Si-CnF2n+1 in the presence of a Lewis base.

公开(公告)号：JPH06228030A

公开(公告)日：1994-08-16

申请号：JP4065893

申请日：1993-02-05

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  HAGIWARA TOSHINORI

IPC: C07B61/00 ,  C07C29/64 ,  C07C33/44 ,  C07C33/46 ,  C07C33/48 ,  C07C41/30 ,  C07C43/178 ,  C07F7/18

Abstract: PURPOSE:To provide the subject compound useful as an important synthetic intermediate for medicines, agrichemicals and functional materials by reacting a carbonyl compound with a 1,2-disilyltetrafluoroethane compound and, if desired, subsequently hydrolyzing the reaction product. CONSTITUTION:A carbonyl compound of formula: R R C-O (R ,R are H, alkyl, aromatic, aralkyl, alkenyl, alkinyl, or R and R together form a ring) is reacted with a 1,2-disilyltetrafluoroethane compound of formula I (R -R are alkyl, aromatic), and the reaction product is, if desired, hydrolyzed to produce the alcohol derivative having a fluorine-containing atomic group at the alpha-position and represented by formulas II, III and/or IV. A reaction accelerator (especially preferably a fluoride ion-source or a metal alkoxide) is preferably used in the reaction. The reaction product is useful as a synthetic intermediate for medicines or agrichemicals such as anticancer agents or enzyme-inhibiting agents, and functional materials such as fluorine-containing polymers or ferrodielectric liquid crystals. The reaction proceeds under mild conditions with easy reactional operation.