公开(公告)号：JPH03236369A

公开(公告)日：1991-10-22

申请号：JP3221490

申请日：1990-02-13

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D295/10 ,  C07C333/14 ,  C07D213/82

Abstract: PURPOSE:To readily and quickly obtain a compound useful as a fog restrainer for silver halide photograph in high yield by treating an amide-type compound with sodium hydrogenate and iodine and reacting with dithiocarbamate. CONSTITUTION:An amide-type compound expressed by formula I(R is aryl, heterocycle group, alkyl, dialkylamino or alkoxy) is dissolved in a suitable solvent (e.g. THF) and sodium hydrogenate is added, then stirred at room temperature, thus iodine is further added and stirred. Next, dithiocarbamate expressed by formula II(R and R are lower alkyl, formable of a ring with bonding; M is metallic cation) in an amount of 1-1.2 equiv. to iodine is added to the system and resultant system is stirred at room temperature for 1-2hr to afford the aimed compound expressed by formula III. 1-0.75 equiv. sodium hydrogenate and 0.75-0.5 equiv. iodine are used to 1 equiv. of the compound expressed by formula I.

公开(公告)号：JPH02272445A

公开(公告)日：1990-11-07

申请号：JP9414989

申请日：1989-04-13

Applicant: AGENCY IND SCIENCE TECHN ,  KONISHIROKU PHOTO IND

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI ,  HIRABAYASHI SHIGETO ,  KANEKO YUTAKA

IPC: G03C1/34 ,  C07C327/26 ,  C07C327/36 ,  C07C329/00 ,  C07C329/04 ,  C07C329/14 ,  C07C333/04 ,  C07C333/18 ,  C07D213/81 ,  C07D295/20

Abstract: PURPOSE:To suppress the generation of a fogging during long-term preservation or in spite of storage at a high temp. or at and under a high temp. and high humidity and to prevent the degradation in sensitivity and the softening of gradation by adding and incorporating the fogging restrainer consisting of specific compds. into silver halide emulsion layers or the hydrophilic colloidal layers adjacent thereto. CONSTITUTION:At least one of the compds. expressed by general formula [I] are incorporated into at least one layer of the silver halide emulsion layers and the hydrophilic colloidal layers adjacent thereto. The alkyl groups expressed by R1, R2 in the compds. expressed by the general formula [I] are exemplified by, for example, a methyl group, ethyl group, propyl group, butyl group, hexyl group, dodecyl group, octadecyl group, etc., of 1 to 20C (preferably 1 to 8C) alkyl. These compds. are dissolved in water or hydrophilic org. solvent and are added to required constituting layers. The most preferable period of the addition is at the end of the chemical aging of the silver halide emulsion.

公开(公告)号：JPH02235879A

公开(公告)日：1990-09-18

申请号：JP5588089

申请日：1989-03-08

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YASUMOTO MASAHIKO ,  TSUCHIYA TORU ,  SHIBUYA ISAO ,  GOTO MIDORI

IPC: A01N47/28 ,  A61K31/54 ,  C07D285/34

Abstract: NEW MATERIAL:A 2,6-bis(disubstituted amino)-4-dialkylthiocarbamoylimino-1,3,5- thiadiazine of formula I (R1 and R2 are each alkyl and may be linked to form a ring). EXAMPLE:2,6-bis(dimethylamino)-4-dimethylthiocarbamoylimino-1,3,-5-thi adiazine. USE:Useful for medicines, pesticides and as an intermediate. PREPARATION:A N,N-disubstituted cyanamide of formula II is reacted together with carbon disulfide at increased pressure to obtain the compound of the formula I. The molar ration of the compound of the formula II to the carbon disulfide is normally (1:10) - (10:1), although the stoichiometric molar ratio is 3:1. Higher pressure is preferable, but normally being 1,000 - 9,000atom. The reaction temperature is pref. 20 - 160 deg.C.

公开(公告)号：JPH0267276A

公开(公告)日：1990-03-07

申请号：JP21973788

申请日：1988-09-02

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D327/04 ,  C07B47/00 ,  C07D285/00 ,  C07D285/15 ,  C07D291/06 ,  C07D339/06 ,  C07D513/04

Abstract: PURPOSE:To simply and quickly obtain the title compound which is a compound useful in organic synthesis under mild reaction conditions in high yield by treating a heterocyclic cation compound using an extremely inexpensive iodine- ammonia mixture system as a raw material. CONSTITUTION:A heterocyclic cation compound expressed by formula I (X and Y are hetero atoms; R is H or substituent group inert to reaction; Z is paired anion; or numbers of ring member in cation part are 5 and X and R may be coupled with covalent bond) is reacted with an iodine-ammonia mixture system in a solvent such as acetonitrile or methanol to provide the ring enlarged product (numbers of ring member: 6) by a nitrogen atom expressed by formula II. In the above-mentioned reaction, the compound expressed by formula I and equivalent molar iodine or triiodide expressed by formula III (numbers of ring member in cation part are 5) are dissolved in a solvent and then excess ammo nia water is added thereto or the compound expressed by formula I is added to the mixture system consisting of iodine in a solvent and excess ammonia water.

公开(公告)号：JPH0267275A

公开(公告)日：1990-03-07

申请号：JP21973888

申请日：1988-09-02

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI

IPC: C07D285/00 ,  C07D285/01

Abstract: PURPOSE:To simply obtain the title compound useful as an antiblushing agent, etc., without using a special raw material in good yield by subjecting N-acyl-S- thioalloylsulphenamide, etc., used as an inexpensive and readily available raw material to cyclo-dehydration in the presence of a strong acid. CONSTITUTION:N-Acyl-S-thioalloylsulphenamide or N-acyl-S-(thioalkoxythio- carbonyl)sulphenamide expressed by formula I (R is alkyl or aryl which may have inert substituent group; R is aryl which may have inert substituent group or thioalkoxyl) and used as a raw material is retained at ordinary temperature or heated a little on a water bath in a solvent having strong dehydrating proper ties, e.g., acetic anhydride or phosphoryl chloride in the presence of a strong acid, e.g. perchloric acid or tetrafluoride to provide the compound expressed by formula II (X is strong acid radical of inorganic acid). Furthermore, the compound expressed by formula I is synthesized, e.g., by reacting Grignard reagent with carbon disulfide and then reacting the obtained compound with hydroxylamine-O-sulfonic acid.

公开(公告)号：JPH01226879A

公开(公告)日：1989-09-11

申请号：JP5222788

申请日：1988-03-04

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YASUMOTO MASAHIKO ,  SHIBUYA ISAO

IPC: C07D251/58 ,  C07D251/70

Abstract: PURPOSE:To readily obtain an amino-1,3,5-triazine compound useful as medicines, agricultural chemicals, dyes, etc., in good yield from an inexpensive and stable compound as a raw material without using a solvent, by reacting a formamide with a di-substituted cyanamide under a high pressure. CONSTITUTION:One molecule of a formamide expressed by formula I (R1 is alkyl, aryl, aralkyl or H), such as formamide, is reacted with 3mol. of a di- substituted cyanamide expressed by formula II (R2 and R3 are alkyl or together form a ring), such as 1-piperidinecarbonitrile, at 50-250 deg.C under >=1,000kg/cm , normally as high as 1,000-9,000kg/cm to afford the aimed compound expressed by formula III, such as 2-amino-4,6-di(1-piperidine)1,3,5-triazine. Furthermore, since di-substituted formamides having a di-substituted amino group expressed by formula IV formed as a by-product act as a solvent in completing the reaction for increasing the amount of the aimed compound, use of a solvent in the reaction system is not required.

公开(公告)号：JPS62209069A

公开(公告)日：1987-09-14

申请号：JP5120686

申请日：1986-03-08

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D285/00 ,  A01N43/74 ,  A61K31/41 ,  A61P1/16

Abstract: PURPOSE:To obtain the titled substance useful as a medicine or agricultural chemical or for organic synthetic chemistry in good yield, by reacting a 3-aryl-5- disubstituted amino-1,4,2-dithiazolium salt with an active methylene compound in the presence of a base. CONSTITUTION:A compound expressed by formula I (R is aryl; R and R are lower alkyl or together may link to form a ring; X is acid radical of inorganic strong acid) is reacted with a compound expressed by formula II (R and R are electron attractive group or together may link to form a ring) in the presence of a base, e.g. NaH, NaOH or triethylamine, at 0 deg.C- room temperature to give the aimed compound expressed by formula III. Examples of the preferred combination of the base and solvent include triethylamine/ dichloromethane, NaH/THF, etc.

公开(公告)号：JPS62209068A

公开(公告)日：1987-09-14

申请号：JP5207386

申请日：1986-03-10

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YANAGIYA KOSHIN ,  YASUMOTO MASAHIKO

IPC: C07D271/06

Abstract: PURPOSE:To readily obtain the titled substance useful as an anesthetic agent, analgesic agent, antitussive agent, etc., in good yield, by reacting an aldoxime with a disubstituted cyanamide. CONSTITUTION:An aldoxime expressed by formula I (R is alkyl, aryl, etc.) is reacted with a disubstituted cyanamide expressed by formula II (R and R are alkyl, aryl, etc., or may together link at the terminals thereof), as neces sary, in an inert organic solvent, e.g. THF, benzene, etc., at 50-150 deg.C to afford a 5-amino-3-substituted 1,2,4-oxadiazole expressed by formula III and 5-(N,N- disubstituted guanidino)-3-substituted 1,2,4-oxadiazole (novel substance) expressed by formula IV. In order to mainly obtain the compound expressed by formula III, the compounds expressed by formulas I and II are reacted at =1:2 above-mentioned molar ratio of the compounds expressed by formula I to II under a high pressure for a long time.