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DE2250343A1 - 4,6-DISUBSTITUTED RESORCINE COMPOUNDS - Google Patents

4,6-DISUBSTITUTED RESORCINE COMPOUNDS

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Publication number
DE2250343A1
DE2250343A1 DE19722250343 DE2250343A DE2250343A1 DE 2250343 A1 DE2250343 A1 DE 2250343A1 DE 19722250343 DE19722250343 DE 19722250343 DE 2250343 A DE2250343 A DE 2250343A DE 2250343 A1 DE2250343 A1 DE 2250343A1
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Germany
Prior art keywords
yield
ethanol
analysis
found
hours
Prior art date
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Pending
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DE19722250343
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German (de)
Inventor
Fritz Prof Dr Eiden
A Dipl Chem Schaumburg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
THIEMANN CHEM PHARM FAB
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THIEMANN CHEM PHARM FAB
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Application filed by THIEMANN CHEM PHARM FAB filed Critical THIEMANN CHEM PHARM FAB
Priority to DE19722250343 priority Critical patent/DE2250343A1/en
Priority to FR7335951A priority patent/FR2202692B1/fr
Priority to BE136485A priority patent/BE805838A/en
Priority to NL7313957A priority patent/NL160167C/en
Priority to GB4749673A priority patent/GB1406345A/en
Publication of DE2250343A1 publication Critical patent/DE2250343A1/en
Priority to NL7610797A priority patent/NL7610797A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/86—Ketones containing a keto group bound to a six-membered aromatic ring containing —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/24—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Dr. ing. Waiter Abitz Dr Dioter F. Morf BsDr. ing. Waiter Abitz Dr Dioter F. Morf Bs

Dr.HaP Dr. HaP

8 München 86, h«wmu·«».»8 Munich 86, h «wmu ·« ».»

13- Oktober 1972 120972-BOctober 13, 1972 120972-B

Chem. pharmaz. Fabrik, Dr.'Hermann Thiemann GmbHChem. Pharmaz. Factory, Dr.'Hermann Thiemann GmbH

4628 Lünen/Westf. ' "4628 Lünen / Westf. '"

4,6-disubstituierte Resorcinverbindungen4,6-disubstituted resorcinol compounds

Die Erfindung betrifft neue Resorcinverbindungen der. allgemeinen FormelThe invention relates to new resorcinol compounds of. general formula

N XN X

worin bedeutenin which mean

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X=O oder NH, R1 = H, CH3,X = O or NH, R 1 = H, CH 3 ,

R2 = H, CH3, CarbonyloxyalKyl, -C-NH-NH2,R 2 = H, CH 3 , carbonyloxyalkyl, -C-NH-NH 2 ,

titi

R5 = χR 5 = χ

R2 'R 2 '

R1 R 1

1 2 worin R und R die vorgenannte Bedeutung haben,1 2 where R and R have the aforementioned meaning,

R1* = H,R 1 * = H,

R5 = H oder R3, R6 = H, OH,R 5 = H or R 3 , R 6 = H, OH,

■χ /j
R und R zusammen den Rest ■ χ / j
R and R together do the rest

It Λ It Λ

1 2 worin R und R die vorgenannte Bedeutung haben.1 2 wherein R and R have the aforementioned meaning.

Alkyl bedeutet vorzugsweise Niedrigalkyl, d.h. mit 1 bis Kohlenstoffatomen.Alkyl is preferably lower alkyl, i.e. having 1 to carbon atoms.

409816/1 - 2 - 409816/1 - 2 -

Die neuen Verbindungen sind wertvolle pharmakologisehe Produkte mit psychopharmakologischen, antiphlogistischen, chemotherapeutischen, immunosuppressiven Eigenschaften sowie Herz- und Kreislauf-Wirkung. Einige der Verbindungen sind auch als Zwischenprodukte zur Herstellung von pharmakologisch wirksamen Verbindungen geeignet.The new compounds are valuable pharmacological products with psychopharmacological, anti-inflammatory, chemotherapeutic, immunosuppressive properties as well as cardiovascular effects. Some of the compounds are also used as intermediates in the preparation of pharmacologically effective compounds.

Die erfindungsgemässen neuen Verbindungen können nach dem folgenden Reaktionsschema erhalten werden, wobei die Ausgangsverbindungen selbst auch zum Teil neu sind:The novel compounds according to the invention can after the following reaction scheme, some of the starting compounds themselves being new:

- 3 409816/1132 - 3 409816/1132

120972-B120972-B

O7 N(CH,),,O 7 N (CH,) ,,

R' y d R ' yd

OR'OR '

OR1 OR 1

1 21 2

R , R wie unter I angegeben,R, R as indicated under I,

R7 = H, CH3, CH2-O-CH3.R 7 = H, CH 3 , CH 2 -O-CH 3 .

Die substituierten Acetophenon-Derivate II können mit Amidacetalen oder durch Esterkondensation zu III oder IV umgesetzt werden, die dann entweder direkt oder nach Umwandlung in V durch Erwärmen mit Hydrazin bzw. Hydroxylamin zu I reagieren.The substituted acetophenone derivatives II can with amide acetals or by ester condensation to III or IV, which then either directly or after conversion to V by heating react with hydrazine or hydroxylamine to form I.

409816/1132409816/1132

B e is p i eleExamples

Stufe A:Level A:

4,6-Diacetyl-resorcyl-di(methoxymethylather)4,6-diacetyl-resorcyl-di (methoxymethyl ether)

23»8 g Natriumsalz des 4,6-Diacetylresorcins werden in
250 ml trockenem Tetrahydrofuran mit 17,7 g Chlordlmethylather über Nacht "bei Raumtemperatur gerührt. Dann
versetzt man mit 2 n. Natronlauge und trennt beide Phasen. Die wässrige Phase wird mit Chloroform extrahiert. Die
vereinigten organischen Phasen werden eingedampft und
das Produkt umkristallisiert.23 »8 g of the sodium salt of 4,6-diacetylresorcinol are in
250 ml of dry tetrahydrofuran with 17.7 g of chlorodimethyl ether are stirred overnight at room temperature. Then
2N sodium hydroxide solution is added and the two phases are separated. The aqueous phase is extracted with chloroform. the
combined organic phases are evaporated and
the product recrystallizes.

Ausbeute: 70 $> d.Th.' .
farblose Kristalle, F = 74° G (Äthanol)
Analyse: Ber.: 59,56 $> C Gef.: 59,03 fi GYield: 70 $> d.Th. ' .
colorless crystals, F = 74 ° G (ethanol)
Analysis: Calc .: 59.56 $> C Found: 59.03 fi G

6,38 0Jo H 6,53 1° H6.38 0 Jo H 6.53 1 ° H

Stufe B:Level B:

4 »6-Di(fo-formylacetyl)-resorcyl-di-(methoxy-methyläther)4 »6-Di (fo-formylacetyl) -resorcyl-di- (methoxymethyl ether)

28,2 g 4,6-Diacetyl-resorcyl-di(methoxy-methyläther) werden mit 37,04 g Ameisensäureäthylester in absolutem Äther gelöst und mit 35,1 g trockenem Kaliummethylat 16 Stunden bei Zimmertemperatur gerührt. Das rote Salz wird dann abgesaugt und sofort mit 0,3 η Essigsäure hydrolysiert. Die Kristalle werden schnell abgesaugt, sie sind wenig haltbar,28.2 g of 4,6-diacetyl-resorcyl-di (methoxy-methyl ether) become with 37.04 g of ethyl formate in absolute ether dissolved and with 35.1 g of dry potassium methylate for 16 hours stirred at room temperature. The red salt is then filtered off with suction and immediately hydrolyzed with 0.3 η acetic acid. the Crystals are quickly sucked off, they are not durable,

Ausbeute: 50 $> d.Ih.Yield: $ 50> i.e.

hellgelbe Kristalle, F = 111° C (isopropanol)light yellow crystals, F = 111 ° C (isopropanol)

0 9 8~1 6 / 1 ΐ 3 20 9 8 ~ 1 6/1 ΐ 3 2

120972-B120972-B

IR: 3000, 2900, 1600/cm NMR (CHCl-)t 3,5 (s,6H), 5,33 (s, 4H) 6,36 (d, 2H, J=5Hz), 7,0 (s, 1H), 8,23 (d, 2H, J=5Hz), 8,5 (a, 1H)IR: 3000, 2900, 1600 / cm NMR (CHCl-) t 3.5 (s, 6H), 5.33 (s, 4H) 6.36 (d, 2H, J = 5Hz), 7.0 (s, 1H), 8.23 (d, 2H, J = 5Hz), 8.5 (a, 1H)

Stufe G:Level G:

Benzo(1f 2-b:5 , 4-b ' )-bi-4-pyron B enzo (1 f 2-b: 5, 4-b ') -bi-4-pyrone

33,8 g 4,6-Di(6o-formylacetyl)-resorcyl-di(methoxymethylather) werden in 100 ml 3 η Schwefelsäure auf 100° C erhitzt.33.8 g 4,6-di (6o-formylacetyl) -resorcyl-di (methoxymethyl ether) are heated to 100 ° C in 100 ml of 3 η sulfuric acid.

Ausbeute: 30 °/<> d.Th.Yield: 30 ° / <> of theory

farblose Kristalle, F =325° C (Essigsäure) Analyse: Ber.: 67,30 °/o C Gef.: 67,05 °ß> Ccolorless crystals, F = 325 ° C (acetic acid) Analysis: Calc .: 67.30 ° / o C Found: 67.05 ° ß> C

2,82 Io H 2,8C °/o H2.82 Io H 2.8 C ° / o H

Stufe D:Level D:

4,6-Ώ i(pyrazqlq-3)-resorci η 4,6-Ώ i (pyr azqlq -3) -res orci η

21,4 g Benzo(i,2-b:5,4-b')-bi-4-pyron werden in 300 ml heissem Alkohol gelöst und mit 35,8 g 80 ^iger wässriger Hydrazin-hydrat-Lösung 2 Stunden am Rückfluss gekocht. Nach dem Erkalten saugt man - wenn nötig nach Einengung die ausgefallenen Kristalle ab.21.4 g of benzo (i, 2-b: 5,4-b ') - bi-4-pyrone are in 300 ml dissolved in hot alcohol and mixed with 35.8 g of 80% aqueous Hydrazine hydrate solution refluxed for 2 hours. After cooling down, vacuum - if necessary after narrowing the precipitated crystals.

- 6 409816/1132 - 6 409816/1132

Ausbeute ϊ 85 i° d.Th.Yield ϊ 85 i ° of theory

farblose Kristalle, F = 269° G (Äthanol) Analyse: Ber.: 59,50 °/o C Gef.s 59,55$ Ccolorless crystals, F = 269 ° G (ethanol) Analysis: Calc .: 59.50 ° / o C, found 59.55 ° C

4,16 io H 4,56 io H4.16 io H 4.56 io H

25,15 io Έ 23 110 io Π25.15 io Έ 23 110 io Π

2.
4,6-Di(5-isoxazolo)-resorcin 2.
4,6-di (5-isoxazolo) resorcinol

5,3 g Benzo(1,2-b2 5,4-b!)-bi-4-pyron werden mit 4,2 g Hydroxylamin-hydrochlorid und 5,9 g Kaliumacetat in 100 ml Eisessig 2 Stunden am Rückfluss gekocht. Hach. Einengen versetzt man mit Wasser und saugt ab.5.3 g of benzo (1,2-b2 5,4-b ! ) -Bi-4-pyrone are refluxed with 4.2 g of hydroxylamine hydrochloride and 5.9 g of potassium acetate in 100 ml of glacial acetic acid for 2 hours. Huh. Concentrate is mixed with water and suctioned off.

Ausbeute: 60 i> d.Th.Yield: 60 i> of theory

farblose Kristalle, F = 360° C (DMFA/HgO) uv m v'· 322, 262 nm (Dioxan) Analyse: Ber.: 59,02 $> C Gef. : 59,15 % Ccolorless crystals, mp = 360 ° C (DMFA / HgO) uv m v ' 322, 262 nm (dioxane) analysis: calc .: 59.02 $> C found: 59.15 % C

3,30 io H 3,70 io H3.30 io H 3.70 io H.

11,47 % Ή 11,28 °/> Ή 11.47 % Ή 11.28 ° /> Ή

Z Z , 5-Dimethyl-6-(4,5-dimethylpyrazol-5)-7-hydroxy-chromon, 5-dimethyl-6- (4,5-dimethylpyrazole-5) -7-hydroxy-chromone

27,0 g α,α·,β,β'-Tetramethyl-^enzo-i.6,3.4di(y-pyron27 (hergestellt nach Wittig, Ber. dtsch. ehem. Ges. !59, (1926)) werden in siedendem Äthanol gelöst und mit 35,8 g27.0 g of α, α ·, β, β'-tetramethyl- ^ enzo-i.6,3.4di (y-pyrone27 (made after Wittig, Ber.dtsch. former Ges.! 59, (1926)) are dissolved in boiling ethanol and 35.8 g

4 0 9816/ 1 1324 0 9816/1 132

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80 ^iger wässriger Hydrazin-hydrat-Lösung 2 Stunden riickfliessend gekocht.80% aqueous hydrazine hydrate solution flowing back for 2 hours cooked.

Man lässt die Lösung abkühlen und saugt, wenn nötig nach Einengung, die ausgefallenen Kristalle ab.The solution is allowed to cool and, if necessary after concentration, the precipitated crystals are filtered off with suction.

Ausbeute: 75 # d.Th.Yield: 75 # of theory

farblose Kristalle, F = 360° C (DMP)colorless crystals, F = 360 ° C (DMP)

UV : 328, 316, 273 nm (Dioxan) maxUV: 328, 316, 273 nm (dioxane) Max

Analyse: Ber.: 67,58 # C Gef.: #Analysis: Calc .: 67.58 # C Found: #

5,67 $ H
9,85 1° N- $ 5.67 H.
9.85 1 ° N-

67,67, 92 ?92? 5,5, 53 ?53? 9,9, 77 ?77? * C* C ί Hί H

Stufe A: ·Level A:

3 ,7-Dimeth.yl-benzo( 1 f2-b:5,4-b' )-bi-4-pyron3, 7-Dimeth.yl-benzo (1 f 2-b: 5,4-b ') -bi-4-pyrone

22,2 g 4,6-Dipropionylresorcin werden mit 26,2 g Ν,Ν-Dimethylformamid-dimethylacetal in siedendem absolutem Xylol 2 Stunden rückfliessend erhitzt. Dabei wird das entstehende Methanol abdestilliert. Nach Erkalten saugt man den Niederschlag ab und kristallisiert um.22.2 g of 4,6-dipropionylresorcinol are mixed with 26.2 g of Ν, Ν-dimethylformamide dimethylacetal in boiling absolute Xylene heated to reflux for 2 hours. It will resulting methanol is distilled off. After cooling, the precipitate is filtered off with suction and recrystallized.

Die Cyclisierung zum 4-Pyron erfolgt durch einstündiges Rühren in 3 η Schwefelsäure bei 100° C.The cyclization to the 4-pyrone takes place for one hour Stir in 3 η sulfuric acid at 100 ° C.

Ausbeute: 75 f» d.Th.Yield: 75 f 'of theory

farblose Kristalle, F = 224° C (Essigsäure) Analyse: Ber.: 69,42 $ C Gef.: 67,26 1» Ccolorless crystals, F = 224 ° C (acetic acid) Analysis: Calc .: 69.42 $ C Found: 67.26 1 » C

4,16 1o H 4,33 % H4.16 1o H 4.33 % H.

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Stufe B:
3-Methyl-6-(4-methylpyrazol-3)--7hydroxy--chrotnon Level B:
3-methyl-6- (4-methylpyrazole-3) - 7-hydroxy-chrotnone

24,2 g 3,7-Dimethyl--benzo(i ,2-^:5,4-13' )-bi-4-pyron werden in siedendem Äthanol gelöst und mit 35,8 g 80 ^iger wässriger Hydrazin-hydrat-Lösung 2 Stunden rückfliessend erhitzt. Man lässt die Lösung erkalten und saugt, wenn nötig nach Einengung, die ausgefallenen Kristalle ab.24.2 g of 3,7-dimethyl-benzo (i, 2 - ^: 5,4-13 ') -bi-4-pyrone become dissolved in boiling ethanol and with 35.8 g 80 ^ iger aqueous hydrazine hydrate solution refluxing for 2 hours heated. The solution is allowed to cool and, if necessary after concentration, the precipitated crystals are filtered off with suction.

Ausbeute: 60 fi d.Th.Yield: 60 fi of theory

farblose Kristalle, P= 272° C (Äbhanol) Analyse: Ber.: 65,61 $C Gef.» ' 64,55 $ Ccolorless crystals, P = 272 ° C (ethanol) Analysis: Calculated: 65.61 $ C Found » '$ 64.55 C

4,72 <fo E 5,16 1o H4.72 <fo E 5.16 1o H

10,93 1° N 10,07 1o N10.93 1 ° N 10.07 10 N

4 ,6-I)i(4 4, 6-I) i (4 77th 5-dimethylpyrazol-3-)-resorcin5-dimethylpyrazole-3 -) - resorcinol

5 g α^α''^,ß'-Tetramethyl-Zbenzo-i .6,3 .4-di(Y~pyron27 werden in 50 ml 80 ^igem wässrigen Hydrazin-hydrat 2 Stunden bei 110·° C Badtemperatur gerührt.5 g α ^ α '' ^, ß'-Tetramethyl-Zbenzo-i .6,3 .4-di (Y ~ pyron27 are in 50 ml of 80 ^ aqueous hydrazine hydrate for 2 hours stirred at 110 ° C bath temperature.

Dann versetzt man mit V/asser und säuert mit Essigsäure leicht an. Es scheiden sich Kristalle aus, die abfiltriert werden.Then add water and slightly acidify with acetic acid. Crystals separate out, which are filtered off will.

Ausbeute: 70 °/o d .Th.Yield: 70 ° / o d .TH.

farblose Kristalle, P = 302° C (Äthanol) UVmax: 310, 285, 257, 249 mn (Dioxan) Analyse: Ber.j 64,41 $ C Gef.: 64,62 °/o Ccolorless crystals, P = 302 ° C (ethanol) UV max : 310, 285, 257, 249 mn (dioxane) analysis: Ber.j 64.41 $ C found: 64.62 ° / o C

6,08$H 6,11 ^H$ 6.08 H 6.11 ^ H

18,78 # # · - 18,81 1o N18.78 # # - 18.81 10 N.

409816/1132409816/1132

ίΟίΟ

120972-Β120972-Β

4 ,6-Di(4~methylpyrazol-3)-resorcin4,6-di (4 ~ methylpyrazole-3) resorcinol

5 g 3.7-Mmethyl-benzo(i,2-b:5,4-V)-M-^-Py11On werden in 50 ml 80 tigern wässrigem Hydrazin-hydrat 2 Stunden bei 110° C Badtemperatur gerührt.5 g of 3.7-Mmethyl-benzo (i, 2-b: 5.4-V) -M - ^ - Py 11 One are stirred in 50 ml of 80 tiger aqueous hydrazine hydrate for 2 hours at 110 ° C. bath temperature.

Dann versetzt man mit Wasser und säuert mit Essigsäure leicht an. Es scheiden sich Kristalle aus, die abfiltriert werden.Then water is added and the mixture is acidified with acetic acid slightly on. Crystals separate out and are filtered off.

Ausbeute: 70 $ d.Th.Yield: $ 70 of theory

farblose Kristalle, F = 283° C (Äthanol) Analyse: Ber.: 62,21 c/o C Gef.i 62,34 % Ccolorless crystals, F = 283 ° C (ethanol) Analysis: Calc .: 62.21 c / o C, found at 62.34 % C

5,22 °/o H 5,18 fo H5.22 ° / o H 5.18 % H

20,73 1° N 20,65 1° N20.73 1 ° N 20.65 1 ° N

Stufe A:Level A:

4,6-Di(1,3-propandion-3-carbonsäureäthylester)-4,6-di (1,3-propanedione-3-carboxylic acid ethyl ester) -

resqrcyl-di(methoxymethyläther) r esqrcyl-di (methoxymethyl ether)

28,2 g 4 ,ö-Diacetyl-resorcyl-difmethoxy-rnethyläther) werden mit 73,8 g Oxalsäurediäthylester in absolutem Äther gelöst und mit 35,1 g trockenem Kaliummethylat 16 Stunden bei Zimmertemperatur gerührt. Das rote Salz wird dann abgesaugt und sofort mit 0,3 η Essigsäure hydrolysiert. Die Kristalle werden schnell abgesaugt, sie sind wenig haltbar.28.2 g of 4, δ-diacetyl-resorcyl-difmethoxy-methyl ether) are dissolved with 73.8 g of diethyl oxalate in absolute ether and stirred with 35.1 g of dry potassium methylate for 16 hours at room temperature. The red salt is then filtered off with suction and immediately hydrolyzed with 0.3 η acetic acid. The crystals are sucked off quickly, they are not durable.

409816/1 132409816/1 132

- 10 -- 10 -

120972-B120972-B

Ausbeute: 75 1° d.Th.
gelbe !Tadeln, F = 135° C (Äthanol) IRi 3OOO, 2900, 1740, 1600/cmYield: 75 1 ° of theory
yellow! blame, F = 135 ° C (ethanol) IRi 3OOO, 2900, 1740, 1600 / cm

Analyse: Ber.: 54,77 1° C Gef.: 55,50 1<> CAnalysis: Calc .: 54.77 1 ° C Found: 55.50 1 <> C

5,43 1° H - 5,22 # H5.43 1 ° H - 5.22 # H

Stufe B:Level B:

4,e-DiCS-carbonsäureäthylester-pyrazol-3)-resorcin4, e-DiCS-carboxylic acid ethyl ester-pyrazole-3) -resorcinol

48,2 g 4,6-Di(i,3-propandion-3-carbonsäureäthylester)~ resorcyl-di(methoxymethyläther) werden in siedendem Äthanol gelöst und mit 35,8 g wässriger 80 ^iger Hydrazinhydrat-Lösung 2 Stunden rückfliessend gekocht. Nach Erkalten saugt man die Kristalle ab und er\värmt sie kurze Zeit in einem Gemisch aus 0,3 η HCl Wasser und Äthanol (1:1:1), lässt erkalten und saugt wiederum ab.48.2 g of 4,6-di (i, 3-propanedione-3-carboxylic acid ethyl ester) ~ resorcyl-di (methoxymethyl ether) are in boiling Ethanol dissolved and with 35.8 g of aqueous 80 ^ iger hydrazine hydrate solution Boiled under reflux for 2 hours. After cooling down, the crystals are sucked off and briefly warmed up Time in a mixture of 0.3 η HCl water and ethanol (1: 1: 1), lets cool and sucks again.

Ausbeute: 70 °/o d.Ih.Yield: 70 ° / o d.Ih.

farblose Kristalle, F = 249° C (DMFA/H2O) UVmax: 314, 240 (Dioxan)colorless crystals, F = 249 ° C (DMFA / H 2 O) UV max : 314, 240 (dioxane)

Analyse: Ber.: 56,25 1° C Gef.: 53,99 1° CAnalysis: Calc .: 56.25 1 ° C Found: 53.99 1 ° C

4,20 $ H 4,92 /ο Η$ 4.20 H 4.92 / ο Η

14,58 io Ή 14,13 1° N14.58 io 14.13 1 ° N.

Stufe A: ·Level A:

2-Carbäthoxy--6-a,cetyl-7-oxy-chromon2-carbethoxy-6-a, cetyl-7-oxy-chromone

In einem Dreihalskolben mit Rührer und RückflusskühlerIn a three-necked flask with a stirrer and reflux condenser

409816/1132 — 11 — 409816/1132 - 11 -

120972-B120972-B

werden 6,9 g Natrium in 100 ml absolutem Alkohol gelöst. Dazu gibt man eine Lösung von 9,7 g Diacetylresorcin und 0,0 g Oxalsäurediäthylester in 150 ml siedendem Alkohol. Nach einstündigem Rühren in der Siedehitze Baugt man ab, hydrolysiert mit 100 ml 3 η Schwefelsäure und cyclisiert dann in Alkohol mit Schwefelsäure durch zweistündiges Erhitzen.6.9 g of sodium are dissolved in 100 ml of absolute alcohol. A solution of 9.7 g of diacetylresorcinol and 0.0 g of diethyl oxalate in 150 ml of boiling alcohol. After stirring for one hour at the boiling point, hydrolyzed with 100 ml of 3 η sulfuric acid and then cyclized in alcohol with sulfuric acid for two hours Heat.

Ausbeute: 70 °/o d.Th.Yield: 70 ° / o of theory

farblose Kristalle, F = 158° C (Äthanol) Analyse: Ber.: 60,87 1° 0 Gef.: 59,96 °/o Ccolorless crystals, mp = 158 ° C (ethanol) analysis: calc .: 60.87 1 ° 0 found: 59.96 ° / o C

4,j58 1o H 4,45 c/° H4, j58 1o H 4.45 c / ° H

Stufe B:Level B:

2 ,8-Dicarbäthoxy-benzo( 1 ,2-b:5,4-b' )-bi-4-pyron 2, 8-dicarbethoxy-benzo (1, 2-b: 5,4-b ') -bi-4-pyro n

In einem Dreihalskolben mit Rührer und Rückflusskühler werden 13,8 g Natrium in 100 ml absolutem Alkohol gelöst Dazu gibt man eine Lösung von 27,6 g 2-Carbäthoxy-6-acetyl-7-oxy-chromon und 16,ι g Oxalsäurediäthylester in 150 ml Alkohol. Nach einstündigem Rühren in der Siedehitze saugt man ab, hydrolysiert mit 100 ml 3 η Schwefelsäure und cyclisiert dann in Alkohol mit Schwefelsäure durch zweistündiges Erhitzen.13.8 g of sodium are dissolved in 100 ml of absolute alcohol in a three-necked flask equipped with a stirrer and reflux condenser A solution of 27.6 g of 2-carbethoxy-6-acetyl-7-oxychromone is added and 16. ι g of diethyl oxalate in 150 ml of alcohol. After stirring for one hour at the boiling point it is suctioned off and hydrolyzed with 100 ml of 3 η sulfuric acid and then cyclized in alcohol with sulfuric acid by heating for two hours.

Ausbeute: 50 % d.Th.Yield: 50 % of theory

farblose Kristalle, P = 233° C (Äthanol)colorless crystals, P = 233 ° C (ethanol)

Analyse: Ber.: 60,34 ■ °/° C Gef.: 59,37 # 0Analysis: Calc .: 60.34 ■ ° / ° C Found: 59.37 # 0

3,94 fo H 4,13 1> H3.94 fo H 4.13 1> H

409816/1132409816/1132

- 12 -- 12 -

120972-B120972-B

Stufe CjLevel Cj

4-(5-Carbonsäureäthylester-pyrazol-3)-6-(5-carbonsäure-4- (5-carboxylic acid ethyl ester-pyrazole-3) -6- (5-carboxylic acid-

hydrazid-pyrazol-3)-resorcinhydrazide-pyrazole-3) resorcinol - .-.

35,8 g 2,8-Dicarbäthoxy-benzod,2-b:5,4-b')-ti-4-pyron werden in siedendem Äthanol gelöst und mit 35,8 g 80 $ wässriger Hydrazin-hydrat-Lösung 2 Stunden rückfliessend erhitzt. Die Lösung lässt man erkalten und saugt, wenn nötig nach Einengen, die ausgefallenen Kristalle ab.35.8 g of 2,8-dicarbethoxy-benzod, 2-b: 5,4-b ') - ti-4-pyrone are dissolved in boiling ethanol and with 35.8 g 80 $ aqueous hydrazine hydrate solution refluxing for 2 hours heated. The solution is allowed to cool and, if necessary after concentration, the precipitated crystals are filtered off with suction.

Ausbeute: 50 % d.Th.Yield: 50 % of theory

farblose Nadeln, I1 = 290° C (Äthanol/Wasser) 316, 240 nm(Dioxan)colorless needles, I 1 = 290 ° C (ethanol / water) 316, 240 nm (dioxane)

Analyse; Ber.: 51,61 1» 0 Gef.j 49,76 ?6 CAnalysis; Ber .: 51.61 1 » 0 found j 49.76? 6 C

4,06 io H 4,52 io H4.06 io H 4.52 io H.

22,57 $> N 21,02 °ß> N $ 22.57> N 21.02 ° ß> N.

2,3-Pimethyl-6(3,4-dimethyl-isoxazol'-5)-7-hyd20xychromon2,3-Pimethyl-6 (3,4-dimethyl-isoxazol'-5) -7-hyd20xychromone

6,7'6 gCjO1 ,ß^'-Tetramethyl-^Benzo-i .6,3 ^-diCY-pyron werden mit 4,2 g Hydroxylamin-hydrochlorid und 5,9 g Kaliumacetat in 100 ml Eisessig 2 Stunden am Rückfluss gekocht.6.7'6 gCjO 1 , ß ^ '- Tetramethyl- ^ Benzo-i .6,3 ^ -diCY-pyrone are refluxed with 4.2 g of hydroxylamine hydrochloride and 5.9 g of potassium acetate in 100 ml of glacial acetic acid for 2 hours cooked.

Nach Einengen versetzt man mit Wasser und saugt ab.After concentration, water is added and the mixture is filtered off with suction.

Ausbeute: 50 $6 d.Th.Yield: 50 $ 6 of that.

farblose Blättchen, 1 = 307° C (Äthanol)colorless leaves, 1 = 307 ° C (ethanol)

09.816/1 132 - 13 -09.816 / 1 132 - 13 -

120972-B120972-B MO, 250MO, 250 nm (Dioxan)nm (dioxane) ,36 5, 36 5 Gef.:Found: 6767 ,44 "/ .44 "/ UVmex' - UV mex '- Ber.:Ber .: 6767 ,30 ?, 30? 55 ,23 "ι , 23 "ι Analyse»Analysis" 55 ί C ί C 44th ,90 ?, 90? 44th 6 Η6 Η ,91 "/> N, 91 "/> N S CS C S HS H 6 N6 N.

1010

3-Methyl-6(4-methylisoxazol-5)~7-hydroxy-chrori)on3-methyl-6 (4-methylisoxazol-5) ~ 7-hydroxy-chrorion) one

6,1 g 3,7-Dimethyl-benzo(i,2-b:5,4-b')-bi-J|-pyron werden mit 4,2 g Hydroxylamin-hydrochlorid und 5,9" g Kaliumacetat in 100 ml Eisessig 2 Stunden am Rückfluss gekocht. Nach Einengen versetzt man mit Wasser und saugt ab.6.1 g of 3,7-dimethyl-benzo (i, 2-b: 5,4-b ') - bi-J | -pyrone with 4.2 g of hydroxylamine hydrochloride and 5.9 "g of potassium acetate boiled under reflux in 100 ml of glacial acetic acid for 2 hours. After concentration, water is added and the mixture is filtered off with suction.

Ausbeute : 50 $> d.Th.
farblose Nadeln, P = 266° G (Äthanol) Analyse: Ber.: 65,37 °ß> C Gef.: 64,98 # CYield: 50 $> d.Th.
colorless needles, P = 266 ° G (ethanol) Analysis: Calc .: 65.37 ° ß> C Found: 64.98 # C

4,31 * H 4,41 % H4.31 * H 4.41 % H.

5,44 $> N 5,43 $> N $ 5.44> N $ 5.43> N.

1111

4,6-Di(3,4-dimethyl-isoxazol-5)-resorcin4,6-di (3,4-dimethyl-isoxazole-5) resorcinol

27,03 g a^'.ß.ß'
werden mit 10,5 g einer ca. 70 $igen äthanolischen Hydroxylaminlösung 2 Stunden bei 100° Badtemperatur gerührt. Nach dem Abkühlen versetzt man mit Wasser.27.03 ga ^ '. Ss.ß'
are stirred with 10.5 g of an approximately 70 $ strength ethanolic hydroxylamine solution for 2 hours at 100 ° bath temperature. After cooling, water is added.

Ausbeute: 50 $ d.Th.Yield: 50 $ of theory

409816/1132409816/1132

16/1 13 14 -16/1 13 14 -

T2O972-BT2O972-B

farblose Kristalle, F = 297° G (Äthanol)colorless crystals, F = 297 ° G (ethanol)

Analyse: Ber.: . 63,99 °/° C Gef»: 63,86 $ CAnalysis: Ber .:. 63.99 ° / ° C Gef »: 63.86 $ C

5,37 io H 5,47 °ß> H5.37 io H 5.47 ° β> H.

9,33 i° N - 9,31 # N9.33 ° N - 9.31 # N

1212th

1,3,5-Tri(pyrazol-3)-2,4,6-trib.ydroxy-benzol1,3,5-tri (pyrazole-3) -2,4,6-trib.ydroxy-benzene

5,0 g Benzo(i,2-b:3,4-b':5}6-b")-tri-4-pyron werden in 100 ml 80 ^igem wässrigem .Hydrazinhydrat gelöst und 1 Stunde bei 100° G gerührt. Dann wird mit 3 η Essigsäure versetzt, der Niederschlag aus Eisessig/Wasser oder 0,1 η Natronlauge umgefällt.5.0 g of benzo (i, 2-b: 3,4-b ': 5} 6-b ") - tri-4-pyrone are in 100 ml of 80% aqueous .Hydrazine hydrate dissolved and Stirred at 100 ° G for 1 hour. Then with 3 η acetic acid added, the precipitate from glacial acetic acid / water or 0.1 η sodium hydroxide solution reprecipitated.

Ausbeute: 50 i> d.Th.·
hellgelbe kristalle, F = 360° G UY ϊ 306 nm (Essigsäure)
Analyse: Ber.: 55,56 $ C Gef.:Yield: 50 i> of theory
light yellow crystals, F = 360 ° G UY ϊ 306 nm (acetic acid)
Analysis: Calc .: 55.56 $ C Found:

3,73 ioE 24,91 io N3.73 ioE 24.91 io N

4 ,6-I)i(^-nitrilo-acetyl)-resorcin4, 6-I) i (^ - nitrilo-acetyl) -resorcinol

4 ,6-Di(5-carbonsäureäthylester-pyrazol-3)-resorcin wird mit überschüssigem Natriumalkoholat 30 Minuten in Äthanol rückfliessend erhitzt. Nach Einengen und Ansäuern sauet man ab.4,6-Di (5-carboxylic acid ethyl ester-pyrazole-3) -resorcinol is refluxed with excess sodium alcoholate in ethanol for 30 minutes. After narrowing and Acidification is done by saucing.

1J 321J 32

5252 ,20 ?, 20? 33 ,80 ?, 80? 2323 ,4 0J , 4 0 y ο G ο G 1o H 1 o H ο Ν ο Ν

120972-B120972-B

Ausbeute: 40 $ d.Th.
gelbe Kristalle, P = >36O° C (Äthanol) IR: 2950, 2200, 1630/cmYield: 40 $ of theory
yellow crystals, P => 360 ° C (ethanol) IR: 2950, 2200, 1630 / cm

Analyse: Ber.: 59,02$ C Gef.: 58,00 $ CAnalysis: Calculated: $ 59.02 C Found: $ 58.00 C

3,30 fo H 2,88 $ H3.30 fo H $ 2.88 H

11,47 ?■> N 12,33 $ N11.47 ? ■> N $ 12.33 N

1414th

2,8-Di(N-hydroxyäthylcarbonsäureamid)-benzo(1,2-b:5,4-b')■2,8-Di (N-hydroxyethylcarboxamide) benzo (1,2-b: 5,4-b ') ■

bi-4-pyron b i-4 pyrone

35,8 g 2,8 Dicarbäthoxy-benzod,2-b:5,4-b')-bi-4-pyron werden in siedendem Äthanol gelöst und mit 13»4 g 2-Aminoäthanol 2 Stunden rückfliessend erhitzt. Die Lösung lässt man erkalten und saugt, wenn nötig nach Einengen, die ausgefallenen Kristalle ab.35.8 g of 2,8-dicarbethoxy-benzod, 2-b: 5,4-b ') - bi-4-pyrone are dissolved in boiling ethanol and refluxed with 13 »4 g of 2-aminoethanol for 2 hours. the The solution is allowed to cool and, if necessary after concentration, the precipitated crystals are suctioned off.

Ausbeute: 50 io d.Th.Yield: 50 io of theory

gelbe kristalle, F = 226° C (Äthanol) UVm : 379, 289, 258 mn (Dioxan)yellow crystals, F = 226 ° C (ethanol) UV m : 379, 289, 258 mn (dioxane)

Analyse: Ber.: 55,67$ C Gef.:Analysis: Calc .: 55.67 $ C Found:

4,15 $ H
7,21 io N$ 4.15 H.
7.21 io N

5050 ,10, 10 Jb C Jb C 44th ,90, 90 σ/ο H σ / ο H 88th ,10 5, 10 5 1O Ή 1 O Ή

409816/ 1132409816/1132

- 16 -- 16 -

Claims (1)

120972-B120972-B Pat entans pruchPat entans pruch Resorcinverbindungen der allgemeinen FormelResorcinol compounds of the general formula HOHO worin bedeuten X=O oder NH,where X = O or NH, R ~ H , CH-, ,R ~ H, CH-,, 2 J 2 y R=H, CH,, Carbonyloxyalkyl,R = H, CH ,, carbonyloxyalkyl, -C-NH-NH2,-C-NH-NH 2 , = χ= χ 11 worin R und R die vorgenannte Bedeutung haben,where R and R have the aforementioned meaning, 409816/1132409816/1132 - 17 -- 17 - 120972-B120972-B 22B034322B0343 H,H, H oder R5, H or R 5 , H, OHH, OH 44th R und R zusammen den RestR and R together do the rest 0 tt C0 dd C .R".R " 11 worm R und R die vorgenannte Bedeutung haben. worm R and R have the aforementioned meaning . 40981 6/113240981 6/1132
DE19722250343 1972-10-13 1972-10-13 4,6-DISUBSTITUTED RESORCINE COMPOUNDS Pending DE2250343A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE19722250343 DE2250343A1 (en) 1972-10-13 1972-10-13 4,6-DISUBSTITUTED RESORCINE COMPOUNDS
FR7335951A FR2202692B1 (en) 1972-10-13 1973-10-09
BE136485A BE805838A (en) 1972-10-13 1973-10-09 NEW RESORCINOL DERIVATIVES AND THEIR PHARMACEUTICAL APPLICATIONS
NL7313957A NL160167C (en) 1972-10-13 1973-10-10 PROCESS FOR THE PREPARATION OF PHARMACEUTICAL PREPARATIONS BASED ON ISOXAZOLE AND / OR PYRAZOLE DERIVATIVES, THE PREPARATIONS FORMED AND A PROCESS FOR THE PREPARATION OF THE ACTIVE COMPOUNDS.
GB4749673A GB1406345A (en) 1972-10-13 1973-10-11 Pharmaceutical preparations comprising substituted resorcinols
NL7610797A NL7610797A (en) 1972-10-13 1976-09-29 PROCEDURE FOR PREPARING PHARMACEUTICAL PREPARATIONS BASED ON 4.6-DIG-SUBSTITUTED RESORCINOL COMPOUNDS.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722250343 DE2250343A1 (en) 1972-10-13 1972-10-13 4,6-DISUBSTITUTED RESORCINE COMPOUNDS

Publications (1)

Publication Number Publication Date
DE2250343A1 true DE2250343A1 (en) 1974-04-18

Family

ID=5859002

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19722250343 Pending DE2250343A1 (en) 1972-10-13 1972-10-13 4,6-DISUBSTITUTED RESORCINE COMPOUNDS

Country Status (5)

Country Link
BE (1) BE805838A (en)
DE (1) DE2250343A1 (en)
FR (1) FR2202692B1 (en)
GB (1) GB1406345A (en)
NL (2) NL160167C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6743815B2 (en) 1998-08-07 2004-06-01 Chiron Corporation Estrogen receptor modulators

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0315111D0 (en) 2003-06-27 2003-07-30 Cancer Rec Tech Ltd Substituted 5-membered ring compounds and their use
WO2010121963A1 (en) 2009-04-21 2010-10-28 Nerviano Medical Sciences S.R.L. Resorcinol derivatives as hsp90 inhibitors

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6743815B2 (en) 1998-08-07 2004-06-01 Chiron Corporation Estrogen receptor modulators
US6869969B2 (en) 1998-08-07 2005-03-22 Chiron Corporation Estrogen receptor modulators

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NL160167C (en) 1979-10-15
NL7610797A (en) 1977-01-31
FR2202692B1 (en) 1977-03-11
NL160167B (en) 1979-05-15
BE805838A (en) 1974-02-01
NL7313957A (en) 1974-04-16
FR2202692A1 (en) 1974-05-10
GB1406345A (en) 1975-09-17

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