NO143531B - PROCEDURE FOR PREPARING ACYLATED BENZOCSAZOLINON DERIVATIVES - Google Patents
PROCEDURE FOR PREPARING ACYLATED BENZOCSAZOLINON DERIVATIVES Download PDFInfo
- Publication number
- NO143531B NO143531B NO742310A NO742310A NO143531B NO 143531 B NO143531 B NO 143531B NO 742310 A NO742310 A NO 742310A NO 742310 A NO742310 A NO 742310A NO 143531 B NO143531 B NO 143531B
- Authority
- NO
- Norway
- Prior art keywords
- derivatives
- group
- lower alkyl
- benzocsazolinon
- procedure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- ASSKVPFEZFQQNQ-UHFFFAOYSA-N 2-benzoxazolinone Chemical class C1=CC=C2OC(O)=NC2=C1 ASSKVPFEZFQQNQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QRMRRLXXFHXMBC-UHFFFAOYSA-N 3-methyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C)C2=C1 QRMRRLXXFHXMBC-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P25/00—Drugs for disorders of the nervous system
- A61P25/04—Centrally acting analgesics, e.g. opioids
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for The present invention relates to a method for
fremstilling av acylerte benzoksazolinonderivater med den generelle formel preparation of acylated benzoxazolinone derivatives of the general formula
hvori in which
R^står for hydrogenatom, en lavere alkylgruppe, en halo- R^ stands for hydrogen atom, a lower alkyl group, a halo-
genert lavere alkylgruppe, en fenylgruppe, en benzylgruppe eller en tienylgruppe, og generic lower alkyl group, a phenyl group, a benzyl group or a thienyl group, and
1*2 står for et' hydrogenatom eller en lavere alkylgruppe, og som er egnet for fremstilling av 5-acyl-2-aminofenoler ved ringåpning, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at man i nærvær av polyfosforsyre omsetter benzoksazolinon eller et N-alkyl-derivat derav, med heksametylen - tetramin eller en organisk syre R^-COOH eller et anhydrid eller klorid derav, hvori R, har den ovennevnte betydning. Disse trekk ved oppfinnelsen fremgår av patent- 1*2 stands for a hydrogen atom or a lower alkyl group, and which is suitable for the production of 5-acyl-2-aminophenols by ring opening, and the peculiarity of the method according to the invention is that in the presence of polyphosphoric acid, benzoxazolinone or a N-alkyl derivative thereof, with hexamethylene - tetramine or an organic acid R^-COOH or an anhydride or chloride thereof, wherein R has the above meaning. These features of the invention appear from the patent
kravet. the requirement.
Foretrukne forbindelser er forbindelser hvori Preferred compounds are compounds in which
R^er et hydrogenatom, et metylradikal, klormetyl, etyl, R^ is a hydrogen atom, a methyl radical, chloromethyl, ethyl,
fenyl, benzyl eller tienyl og phenyl, benzyl or thienyl and
R2er H eller CH3. R 2 is H or CH 3 .
Acyleringsreaksjonen gjennomføres i nærvær av polyfosforsyre, The acylation reaction is carried out in the presence of polyphosphoric acid,
idet de vanlige katalysatorer for Friedel-Craft-reaksjon enten fører til mangfende reaksjon eller ytterst dårlige ut- as the usual catalysts for the Friedel-Craft reaction either lead to a poor reaction or extremely poor results
bytter, og polyfosforsyren spiller under reaksjonen rollen som katalysator og oppløsningsmiddel. changes, and the polyphosphoric acid plays the role of catalyst and solvent during the reaction.
De forbindelser som fremstilles ved hjelp av fremgangsmåten i henhold til oppfinnelsen er utgangsmaterialer innenfor diverse områder av den kjemiske industri, særlig den farma-søytiske industri. De er egnet for fremstilling av forbindelser som ellers bare lar seg fremstille med større vanskeligheter, som f.eks. 5-acyl-2-aminofenoler med den generelle formel The compounds produced using the method according to the invention are starting materials in various areas of the chemical industry, particularly the pharmaceutical industry. They are suitable for the production of compounds that can otherwise only be produced with greater difficulty, such as e.g. 5-acyl-2-aminophenols of the general formula
hvori R^og R2har den tidligere angitte betydning. De nevnte fenoler oppnås enkelt ved hydolyseåpning av den hete-rocykliske ring i benzoksazolinon-derivatene som fremstilles ved fremgangsmåten i henhold til den foreliggende oppfinnelse, og de nevnte fenoler fremviser analgetiske, antifungale og/ eller antimikrobielle egenskaper. wherein R 1 and R 2 have the previously indicated meaning. The mentioned phenols are easily obtained by hydrolysis opening of the heterocyclic ring in the benzoxazolinone derivatives which are produced by the method according to the present invention, and the mentioned phenols exhibit analgesic, antifungal and/or antimicrobial properties.
De følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
Eksem<p>_<el>_l2§Z§£§ty<_>l3benzoksazolinon Eczema<p>_<el>_l2§Z§£§ty<_>l3benzoxazolinone
Til en oppløsning av 5.40 g (0.04 mol) benzoksazolinon i polyfosforsyre (100 g) tilsettes sakte og under omrøring 3.60 g (0.06 mol) eddiksyre. Blandingen oppvarmes gradvis til 100°C og denne temperatur holdes i to timer. Etter avkjøling helles reaksjons- blandingen ut i isblandet vann - og omrøres kraftig. Det oppnådde bunnfall tørkes og omkrystalliseres fra 95% etylalkohol. To a solution of 5.40 g (0.04 mol) benzoxazolinone in polyphosphoric acid (100 g) add slowly and with stirring 3.60 g (0.06 mol) acetic acid. The mixture is gradually heated to 100°C and this temperature is maintained for two hours. After cooling, the reaction mixture is poured into ice-cold water - and stirred vigorously. The precipitate obtained is dried and recrystallized from 95% ethyl alcohol.
Smeltepunkt 228°C Utbytte: 6 6%. Melting point 228°C Yield: 6 6%.
Eksemp_el_2_: 6-f ormYl^S-mety^-benzoksazolinon^ Example_el_2_: 6-formyl^S-methyl^-benzoxazolinone^
Til en oppløsning av 5.96 g (0.04 mol) av 3-metyl-benzoksazolinon i 100 g polyfosforsyre tilsettes 8.40 g (0.06 mol) av heksametylen-tetramin. Blandingen bringes til 150°C og omrøres i 10 minutter ved denne temperatur.. Det avkjøles hurtig og reaksjonsblandingen helles ut i isblandet vann under kraftig omrøring. Det oppnådde bunnfall isoleres, vaskes med vann og tørres. To a solution of 5.96 g (0.04 mol) of 3-methyl-benzoxazolinone in 100 g of polyphosphoric acid, 8.40 g (0.06 mol) of hexamethylene tetramine is added. The mixture is brought to 150°C and stirred for 10 minutes at this temperature. It is cooled rapidly and the reaction mixture is poured into ice-mixed water with vigorous stirring. The resulting precipitate is isolated, washed with water and dried.
Moderlutene behandles flere ganger med eter. Eterløsning-ene forenes, vaskes med vann og tørres over natriumsulfat. Eteren avdampes. Det oppnås en ytterligere fraksjon av produktet som forenes med den første. Det omkrystalliseres fra 95% etylalkohol. The mother liquors are treated several times with ether. The ether solutions are combined, washed with water and dried over sodium sulphate. The ether is evaporated. A further fraction of the product is obtained which unites with the first. It is recrystallized from 95% ethyl alcohol.
Utbytte: 65 - 70% Smeltepunkt: 145 - 146°C. Yield: 65 - 70% Melting point: 145 - 146°C.
I den følgende tabell er oppført forbindelser fremstilt i henhold til oppfinnelsen. Forbindelsene nr. 1 til 12 er fremstilt etter fremgangsmåten i eksempel 1 og forbindelsene 13 og 14 ettér fremgangsmåten i eksempél 2. The following table lists compounds produced according to the invention. Compounds no. 1 to 12 are prepared according to the method in example 1 and compounds 13 and 14 according to the method in example 2.
Forbindelsene fremstilt i henhold til oppfinnelsen er i første rekke interessante innenfor forskjellige grener av den kjemiske industri, særlig innenfor den farmasøytiske kjemi, hvor de også muliggjør fremstilling av rekker av forbindelser som vanskelig kan fremstilles på andre måter. The compounds produced according to the invention are primarily of interest within various branches of the chemical industry, particularly within pharmaceutical chemistry, where they also enable the production of a range of compounds which are difficult to produce in other ways.
Forbindelsene fremstilt i henhold til oppfinnelsen tillater f.eks. fremstilling av benzoksazolinoner med forskjellige substituenter i 6-stillingen, spesielt aminerte substituenter, og fører således ved hydrolyse til 5-acyl-2-amino-fenoler. The compounds produced according to the invention allow e.g. production of benzoxazolinones with various substituents in the 6-position, especially aminated substituents, and thus lead to 5-acyl-2-amino-phenols on hydrolysis.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7323280A FR2244506B1 (en) | 1973-06-26 | 1973-06-26 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO742310L NO742310L (en) | 1975-01-20 |
| NO143531B true NO143531B (en) | 1980-11-24 |
| NO143531C NO143531C (en) | 1981-03-11 |
Family
ID=9121568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO742310A NO143531C (en) | 1973-06-26 | 1974-06-25 | PROCEDURE FOR THE PREPARATION OF ACYLATED BENZOCSAZOLINON DERIVATIVES. |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5922711B2 (en) |
| BE (1) | BE816820A (en) |
| CA (1) | CA1019749A (en) |
| CH (2) | CH602679A5 (en) |
| DE (1) | DE2429562A1 (en) |
| DK (1) | DK341274A (en) |
| FR (1) | FR2244506B1 (en) |
| GB (1) | GB1425429A (en) |
| IL (1) | IL45113A (en) |
| LU (1) | LU70403A1 (en) |
| NL (1) | NL179135C (en) |
| NO (1) | NO143531C (en) |
| SE (1) | SE424865B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3039929A1 (en) * | 1980-10-23 | 1982-06-03 | Bayer Ag, 5090 Leverkusen | ISOCYANATO-OXAZOLINONE, A METHOD FOR THE PRODUCTION OF PLASTIC PRECOWERS HAVING OXAZOLIN-2-ONE RINGS AND THE USE THEREOF FOR THE PRODUCTION OF HIGH-MOLECULAR PLASTICS |
| DE3042481A1 (en) * | 1980-11-11 | 1982-06-16 | A. Nattermann & Cie GmbH, 5000 Köln | (OMEGA) - (2-OXO-BENZAZOLINYL) -ALKANIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND PHARMACEUTICAL PREPARATIONS CONTAINING THEM |
| GB8325370D0 (en) * | 1983-09-22 | 1983-10-26 | Fujisawa Pharmaceutical Co | Benzoxazoline and benzothiazoline derivatives |
| FR2645149A1 (en) * | 1989-03-30 | 1990-10-05 | Adir | |
| US5166353A (en) * | 1989-04-28 | 1992-11-24 | Adir Et Compagnie | Benzothiazolinone compounds |
| FR2646350B1 (en) * | 1989-04-28 | 1991-06-28 | Adir | NOVEL BENZOTHIAZOLINON DERIVATIVES, THEIR PREPARATION PROCESS AND THE PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME |
| FR2663633B1 (en) * | 1990-06-22 | 1994-06-17 | Adir | NEW CHALCONES, THEIR PREPARATION PROCESS AND THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM. |
| FR2663634B1 (en) * | 1990-06-22 | 1992-09-04 | Adir | NOVEL ACYL BENZOXAZOLINONES, PROCESS FOR THEIR PREPARATION AND THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM. |
| FR2756825B1 (en) * | 1996-12-10 | 1999-01-08 | Adir | NOVEL [3H] -BENZOXAZOLE-2-THIONES AND [3H] - BENZOTHIAZOLE-2-THIONES DERIVATIVES, THEIR PREPARATION METHOD AND THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM |
| EP1087952B1 (en) | 1998-06-18 | 2004-06-02 | Novartis AG | Benzazole compounds and their use |
| US9540322B2 (en) | 2008-08-18 | 2017-01-10 | Yale University | MIF modulators |
| US9643922B2 (en) | 2008-08-18 | 2017-05-09 | Yale University | MIF modulators |
| EP2326631A4 (en) * | 2008-08-18 | 2012-03-21 | Univ Yale | Mif modulators |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3050526A (en) * | 1960-08-08 | 1962-08-21 | Rohm & Haas | 3-thiocyanomethyl-2-benzothiazolinones and benzoxazolinones |
-
1973
- 1973-06-26 FR FR7323280A patent/FR2244506B1/fr not_active Expired
-
1974
- 1974-06-20 DE DE2429562A patent/DE2429562A1/en not_active Withdrawn
- 1974-06-24 SE SE7408255A patent/SE424865B/en not_active IP Right Cessation
- 1974-06-24 NL NLAANVRAGE7408489,A patent/NL179135C/en not_active IP Right Cessation
- 1974-06-24 GB GB2795274A patent/GB1425429A/en not_active Expired
- 1974-06-25 DK DK341274A patent/DK341274A/da not_active Application Discontinuation
- 1974-06-25 CH CH180477A patent/CH602679A5/xx not_active IP Right Cessation
- 1974-06-25 IL IL45113A patent/IL45113A/en unknown
- 1974-06-25 CH CH372074A patent/CH592642A5/xx not_active IP Right Cessation
- 1974-06-25 CA CA203,335A patent/CA1019749A/en not_active Expired
- 1974-06-25 NO NO742310A patent/NO143531C/en unknown
- 1974-06-25 BE BE145848A patent/BE816820A/en not_active IP Right Cessation
- 1974-06-25 LU LU70403A patent/LU70403A1/xx unknown
- 1974-06-26 JP JP49073743A patent/JPS5922711B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IL45113A0 (en) | 1974-09-10 |
| IL45113A (en) | 1977-06-30 |
| FR2244506B1 (en) | 1977-02-25 |
| CA1019749A (en) | 1977-10-25 |
| DK341274A (en) | 1975-02-24 |
| DE2429562A1 (en) | 1975-01-16 |
| BE816820A (en) | 1974-12-27 |
| JPS5069073A (en) | 1975-06-09 |
| NL179135B (en) | 1986-02-17 |
| NL7408489A (en) | 1974-12-30 |
| NO742310L (en) | 1975-01-20 |
| CH602679A5 (en) | 1978-07-31 |
| SE424865B (en) | 1982-08-16 |
| GB1425429A (en) | 1976-02-18 |
| FR2244506A1 (en) | 1975-04-18 |
| CH592642A5 (en) | 1977-10-31 |
| SE7408255L (en) | 1974-12-27 |
| NO143531C (en) | 1981-03-11 |
| LU70403A1 (en) | 1975-03-27 |
| NL179135C (en) | 1986-07-16 |
| JPS5922711B2 (en) | 1984-05-28 |
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