公开(公告)号：JPS6256939A

公开(公告)日：1987-03-12

申请号：JP19718185

申请日：1985-09-05

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C07F7/10 ,  C07C67/00 ,  C07C201/00 ,  C07C205/06 ,  G02F1/35 ,  G02F1/355 ,  G02F1/361

Abstract: PURPOSE:To obtain the titled material capable of enlarging a SHG and having a stability at room temp. and enabling to easily growing a large monocrystal by selecting the 8 kinds of the compds. defined by the specific table from a specific ethynyl nitrobenzene derivative shown by the formula. CONSTITUTION:The titled material is composed of the ethynyl nitrobenzene derivative shown by the formula and comprises the 8 kinds of the compds. defined by the table. The prescribed derivative is prepared by reacting the corresponding halonitroiodobenzene derivative with the ethynyl derivative in a solvent and in the presence of a bispalladium II chloride catalyst. Thus, the titled material having the larger SHG than that of an urea by a few times and a stable at the room temp. and making an ease to grow a large monocrystal is obtd.

公开(公告)号：JPH07126223A

公开(公告)日：1995-05-16

申请号：JP1792794

申请日：1994-01-17

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C07C205/06 ,  C07C211/52 ,  C08G61/00 ,  C08G61/02

Abstract: PURPOSE:To provide a new compound subject to solid polymerization with the substituents conjugated with diacetyl triple bond, useful for nonlinear optical materials, photosensitive materials, or polymeric semiconductor crystals. CONSTITUTION:The objective phenylbutadiyne derivative of formula I (one of the sites at Rs except R3 is substituted by NO2, the rest of Rs being each H), e.g. 6-(2-nitrophenyl)butadiyne, can be obtained by asymmetric coupling reaction between a phenylacetylene derivative of formula II and 4-bromo-2- methyl-3-butyne-2-ol of formula III followed by deacetonation of the resultant phenyldiacetylene derivative of formula IV using a potassium hydroxide catalyst.

公开(公告)号：JPS62255460A

公开(公告)日：1987-11-07

申请号：JP9595686

申请日：1986-04-25

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C08F38/00 ,  C07C67/00 ,  C07C231/00 ,  C07C233/15

Abstract: NEW MATERIAL:A compound of formula I [one of R1 and R2 is nitro and the other is H; either one of R1'-R3' is -NHCO-(CH2)n-CO2H (n is 6-18) and the others are H]. EXAMPLE:2-(4-(3-Nitrophenyl)-1,3-butadiynyl)phenylcarbamoylnonadecanoic acid. USE:Useful as a monomer of diacetylene compound for forming a nonlinear optical material, a photo-sensitive material or a polymeric semiconductor material. It is polymerizable in solid phase and can form a built-up film. It has an asymmetric structure and high electronic effect. PREPARATION:The compound of formula I can be produced by carrying out asymmetric coupling of bromoethynylnitrobenzene of formula II with an ethynylaniline of formula III and reacting the resultant compound of formula I (one of R1'-R3' is amino and the others are H) with an alkyldicarboxylic acid monochloride of formula IV in the presence of an amine.

公开(公告)号：JPH03251566A

公开(公告)日：1991-11-11

申请号：JP4667390

申请日：1990-02-26

Applicant: TODA KOGYO CORP ,  AGENCY IND SCIENCE TECHN

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  MASAKI ATSUSHI ,  NAKANISHI HACHIRO ,  OSUGI MINORU ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C07D209/86 ,  C07B61/00 ,  C07C15/48 ,  C07D401/06

Abstract: NEW MATERIAL:A compound of formula I [R is 2,5-or 3,5-bis(trifluoromethyl) phenyl, 4-aminophenyl or 2-pyridyl]. EXAMPLE:1-[2,5-bis(trifluoromethyl)phenyl]-5-(N-carbazolyl-1,3-pentadi yne. USE:Useful for functional materials such as nonlinear optical materials, photosensitive materials and polymeric semiconductor crystals. PREPARATION:An asymmetrical coupling is made between (A) an ethynylbenzene derivative of formula II and (B) N-(3-bromo-2-propynyl)carbazole of formula III into the objective compound of the formula I. The reaction is carried out in such a manner that an amine and copper chloride are added to a solution of the compound of the formula II followed by gradual addition of the compound of the formula III while stirring.

公开(公告)号：JPH01233263A

公开(公告)日：1989-09-19

申请号：JP5870688

申请日：1988-03-11

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C07C205/06 ,  C07C67/00 ,  C07C201/00 ,  C07C209/00 ,  C07C211/45 ,  C07C211/52 ,  C07C211/65 ,  C08G61/00 ,  C08G61/02 ,  G02F1/35 ,  G02F1/355 ,  G02F1/361

Abstract: NEW MATERIAL:A compound expressed by formula I (R1 is NO2 or NH2 and R2-R5 are H; R2 is NO2 or NH2 and R1, R3-R5 are H or R1 is NR2, R2 and R3 are H and R4 is NO2). EXAMPLE:1-(2-Nitrophenyl)butadiyne. USE:A nonlinear optical material, photosensitive material or high polymer semiconductor crystals, having great molecular polarization due to nitro group which is an electron attractive group or amino group which is an electron donative group, resulting in expectable great nonlinear optical effects. PREPARATION:A phenylicetylene derivative expressed by formula II and a 4-bromo-2-methyl-3-butyn-2-ol expressed by formula III are subjected to asymmetric coupling reaction to provide a phenyldiacetylene derivative expressed by formula IV, which is then subjected to acetone removing reaction in the presence of potassium hydroxide catalyst to afford the aimed compound expressed by formula I.

公开(公告)号：JPS6368549A

公开(公告)日：1988-03-28

申请号：JP21333886

申请日：1986-09-10

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C08F38/00 ,  C07C67/00 ,  C07C231/00 ,  C07C233/07 ,  C07C233/13 ,  C07C233/15 ,  C07C233/43 ,  C07C233/54 ,  C07C233/56 ,  C07C235/72 ,  C07C235/74 ,  C07C239/00 ,  C07C269/00 ,  C07C271/20

Abstract: NEW MATERIAL:A compound expressed by formula I (n is 0-20; R is alkyl, alkenyl, alkynyl, aryl, alkaryl or aralkyl, provided that those groups contain at least one substituent selected from halogen, amide, urethane, ester and nitro). EXAMPLE:Eicosane di{3-[4-(3-nitrophenyl)butadienyl]anilide}. USE:A monomer having solid phase polymerizability and large electronic effect, and usable and large electronic effect and usable and a functional material such as non-linear optical material, photosensitive material, high polymer semi conductor crystal, etc., as well as cast film. PREPARATION:A diphenyl diacetylene derivative expressed by formula III obtained by subjecting a bromoethynyl derivative expressed by formula II to asynmetric coupling reaction with 3-ethyl aniline in a solvent in the presence of a copper salt catalyst such as copper (I) chloride, etc., is reacted with a dicarboxylic acid dichloride expressed by formula IV in the presence of an amine to provide a compound expressed by formula I.

公开(公告)号：JPS62255459A

公开(公告)日：1987-11-07

申请号：JP9595586

申请日：1986-04-25

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: C08F38/00 ,  C07C67/00 ,  C07C231/00 ,  C07C233/15

Abstract: NEW MATERIAL:A compound of formula I [either one of R1-R3 is -NHCO-(CH2)n-CH3 (n is 12-18) and the others are H]. EXAMPLE:1-(3-Nitrophenyl)-4-(2-heptadecylcarbamoylphenyl)-1,3-butadiyne. USE:Useful as a monomer of diacetylene compound for forming a nonlinear optical material, a photo-sensitive material or a polymeric semiconductor material. It is polymerizable in solid phase and is an aromatic compound having asymmetric structure and having substituent group conjugating with the triple bond of diacetylene. It has high electronic effect. PREPARATION:The compound of formula I can be produced by carrying out asymmetric coupling of 3-(bromoethynyl)nitrobenzene of formula II with an ethynylaniline of formula III (one of R1-R3 is amino and the others are H) and reacting the resultant compound of formula I (one of R1-R3 is amino and the others are H) with carboxylic acid chloride of formula IV in the presence of an amine.

公开(公告)号：JPH02215742A

公开(公告)日：1990-08-28

申请号：JP3702089

申请日：1989-02-16

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  OSUGI MINORU ,  HORAI SHIGERU ,  HORIISHI NANAO

IPC: G02F1/35 ,  C07C43/225 ,  C07C211/29 ,  C07C211/52 ,  C08F38/00 ,  C08F138/00 ,  G02F1/355 ,  G02F1/361

Abstract: NEW MATERIAL:A diphenyldiacetylene derivative expressed by formula I (R1 is H or CH3O; R2 is H, CH3O or CH3NH; R3 and R4 are H or CF3) and having solid-phase polymerizability. EXAMPLE:1-(4-Methoxyphenyl)-4-[2,5-bis(trifluoromethyl)phenyl]-1,3-but adiyne. USE:A functional material, such as nonlinear optical material, photosensitive material or polymer semiconductor crystals. PREPARATION:An ethynylbenzene derivative formula formula II and 1-bromo-3- hydroxy-3-methyl-1-butyne expressed by formula III are subjected to asymmetric coupling and the resultant diacetylene derivative expressed by formula IV is subjected to removal of acetone in the presence of a basic catalyst to provide a phenylbutadiyne derivative expressed by formula V, which is then subjected to coupling reaction with bis(trifluoromethyl)iodobenzene expressed by formula VI in the presence of a palladium catalyst to afford the compound expressed by formula I.

公开(公告)号：JPH01233274A

公开(公告)日：1989-09-19

申请号：JP5870788

申请日：1988-03-11

Applicant: AGENCY IND SCIENCE TECHN ,  TODA KOGYO CORP

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  KATO MASAO ,  HORAI SHIGERU ,  HORIISHI NANAO ,  KINOSHITA MINORU ,  SUGANO TADASHI ,  NOZAWA KIYOKAZU

IPC: C07D211/94 ,  C08F38/00

Abstract: NEW MATERIAL:A diacetylene derivative expressed by formula I (X is NH or O; m is 8-20; n is 4-20). EXAMPLE:4-(10,12-Pentacosadiynylcarbonylamino)-2,2,6,6-tetramethylpipe ridine-1- oxy. USE:A diacetylene monomer, capable of forming paramagnetic polydiacitylene crystals in 100% radical concentration and utilized as a standard marker, antioxidant, radical scavenger, etc., since the monomer has stable radicals and exhibits solidphase polymerizability. PREPARATION:A diacetylenecarboxylic acid compound expressed by formula II and a stable radical compound expressed by formula III are subjected to dehydrating condensation reaction using dicylohexyldicarbodiimide to afford the aimed compound expressed by formula I.

公开(公告)号：JPH045635A

公开(公告)日：1992-01-09

申请号：JP10712190

申请日：1990-04-23

Applicant: AGENCY IND SCIENCE TECHN

Inventor： MATSUDA HIROO ,  OKADA SHUJI ,  NAKANISHI HACHIRO ,  OSUGI MINORU ,  HORAI SHIGERU

IPC: G02F1/35 ,  C08F38/00 ,  G02F1/355 ,  G02F1/361

Abstract: PURPOSE:To obtain the above optical material having a high nonlinear optical characteristic by forming a supporting film consisting of a synthetic resin which can be dissolved in a common solvent for a diacetylene compd. and the diacetylene compd. which is subjected to solid phase polymn. therein to mixing ratios of a prescribed range. CONSTITUTION:This optical material consists of the supporting film consisting of the synthetic resin which can be dissolved in the common solvent for the diacetylene compd. and the diacetylene compd. which is subjected to the solid phase polymn. therein. The mixing ratios based on the volume of the supporting film and the diacetylene compd. are specified to a 5:1 to 1:20 range. Polystyrene, polyvinyl chloride, etc., which are soluble in the common solvent for the diacetylene compd. are used as the synthetic resin to be used in this embodiment. Hexadiindiol-P-toluene sulfonite, etc., are usable as the solid phase polymerizable acetylene compd. The material which is the material having the nonlinear optical characteristic, having optical uniformity, transparency and easy workability including the formation of thinner films, and is the excellent stability with lapse of time is obtd. in this way.