IE822753L - Benzopyran-4-ones - Google Patents

Benzopyran-4-ones

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Publication number
IE822753L
IE822753L IE822753A IE275382A IE822753L IE 822753 L IE822753 L IE 822753L IE 822753 A IE822753 A IE 822753A IE 275382 A IE275382 A IE 275382A IE 822753 L IE822753 L IE 822753L
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hydrogen
benzopyran
formula
methyl
phenyl
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IE822753A
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IE56916B1 (en
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Lipha
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • 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
    • 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
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
    • C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
    • 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
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
    • C07D311/36—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only not hydrogenated in the hetero ring, e.g. isoflavones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Abstract

1. Claims for the Contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE Bromoalkyl-8-4H-[1]-benzopyran-4-ones, characterised by the formula see diagramm : EP0080419,P8,F3 where AR is a methyl, phenyl, methylphenyl, methoxyphenyl, dimethoxyphenyl, thenyl, furyl, napthyl, cyclohexyl or benzyl radical, R1 is hydrogen, Y is hydrogen. 1. Claims for the Contracting State : AT Process for preparing bromoalkyl-8-4H-[1]-benzopyran-4-ones represented by the formula see diagramm : EP0080419,P9,F3 where AR is a methyl, phenyl, methylphenyl, methoxyphenyl, dimethoxyphenyl, thenyl, furyl, naphthyl, cyclohexyl or benzyl radical, R1 is hydrogen and Y is hydrogen, characterised by the ring closure of the 1,3-propanediones of the formula see diagramm : EP0080419,P9,F4 where AR, R1 and Y have the same meanings as previously, R2 is hydrogen or a methyl radical, in the presence of bromhydric acid. [EP0080419A2]

Description

The present invention concerns 8-haLoalky]—411— [1]-benzopyran-4-ones and the preparation thereof. 8-Haloalky1-4H-[1]-benzopyran-4-ones are represented by the formula o CHzBr where AR is a methyl, phenyl, methylphenyl, methoxyphenyl, dimethoxyphenyl, thienyl, furyl, naphthyl, cyclohexyl or benzyl radical, Y is hydrogen, R| is hydrogen.
They are also represented by the said formula I, where AR is a phenyl radical, is hydrogen, Y is a methyl or methoxy radical.
They are also represented by the same formula I, where AR is hydroyen or a phenyl radical, Ri is a phenyl radical, Y is hydrogen.
These compounds can be used as intermediate industrial products for synthesis, in particular in the field of pesticides and pharmaceutical products such as [4-oxo-4Ii-|l]-benzopyran-8-yl] alkanoic acids and their derivatives which are the subject matter of European Patent Application No. 80.934. 8-Bromoalky1-4H- [11 -benzopyran-4-ones constitute a particularly interesting class.
Bromobenzopyranones corresponding to formula I can be prepared, with good yields, by ring closure of the 1,3-propanediones os the formula o o where AR, R1 and V have the same meanings as previously, Rj is hydrogen or a methyl radical, in the presence of hydrobromic acid.
Examples are given below which illustrate the invention in non-restrictive manner.
Example 8 is a reference example and Examples 11 and 16 relate to the preparation of the starting materials for the products of Examples 12 and 17, respectively.
Example 1 : 3-Uromomcthy]-2-phenyl-4II-f1J-bonzopyran-4-one (formula 1) C16HllBr°2' MW = 315.17 A mixture of 361 g (1.40 moles) of 1-(2-hydroxy-3- mcthoxy-methylphenyl)-3-pheny1-1,3-propanedione, 1.4 1 of acetic acid and 917 ml of hydrobromic acid at 62 % is heated for 3 hours at 70°C. It is then poured into 5 1 of cold water, filtered, washed in water and recrystallised in acetone. 207.4 g (Rdt : 47 %) ot a white solid are obtained. PF : 182-183°C. IR : \)c = 0 : 1650 cm"' . NMR (DMSO) Analysis : C % H % Bs: ^ Calculated 60.98 3.51 2S.36 Found 61.12 3.35 25.3< 4 Example 2 : 8-Bromomethyl-2-phenvl-4H- [1]-benzopyran-4-one (formula 1) C16HuBr02. WW = 315.17 5 880 ml of anhydrous dioxane and 84.5 g (1.76 moles) of sodium hydride are placed in a reactor. The environment is brought to 80°C and a mixture of 277 g (1.32 moles) of methyl 3-methoxymethyl-2-methoxy-benzoate and 105.7 g (0.88 mole) of acetophenone lO are added drop by drop with stirring. Heating then ■ continues at 80°C for 3 hours. After cooling, 7 litres of n-hexane are added with stirring. It is left to rest overnight. The precipitate formed is dried, and is introduced in small portions into a mixture : -15 acetic acid : 1.3 litres, - water : 2.6 litres, - benzene : 2.6 litres. The organic phase is decanted, washed with a solution of sodium bicarbonate, dried, and the solvent is evaporated under vacuum. 227 g are obtained of an oil which is used without purification 20 in the next stage. This oil is solubilised in 911 ml of acetic acid. 650 ml of hydrobromic acid at 62 % is added and the environment is brought to 80°C for 3 hours. The mixture is cooled to 40°C and poured with stirring into 12 litres of water. The precipitate 25 formed is filtered, washed in water and recrystallised in acetone. Weight obtained : 123 g (Rdt : 51.3 %), PFG : 182-183°C.
Example 3 : 8-8romomethyl-2-(4-methylphenvl ) -4H-[1]-benzopvran-4-30 one (formula 2) C17H13Br02. MW : 329.20 Prepared according to example 2, starting from 51.1 q (0.38 mole) of 1-(4-methylphenyl)ethanone, 120g 35 (0.571 mole) of methyl 2-methoxy-3-methoxymethy1- s benzoate. After isolation, the oil obtained is recovered with 348 ml of acetic acid and 348 ml of hydrobromic acid at 62 Weight obtained : 53.3 (Rdt : 41.8 %), PFjq : 191°C (toluene), IR : \J c = 0 (pyrone) 5 : 16 Example 4 : 8-Bromomethvl-2-(4-methoxvphenyl)-4H- 111 -benzopvran-4-one (formula 3) C17Hi3Br03. MW = 345.20 Prepared according to example 2, starting from 57. L4 g (0.38 mole) of 1-(4-methoxyphenyl)ethanone, 120g (0.571 mole) of methyl 2-methoxy-3-niethoxyi:iethyl-benzoate. After isolation, the oil obtained is recovered with 457 ml of acetic acid and 325 ml of hydrobromic acid at 62 %. Weight obtained : 78g (Rdt : 59.4 %), PFk : 165°C (toluene). IR : V) c =. 0 (pyrone) : 1640 cra-^. NMR (CDCI3) in ppm with respect to the TMS, 3 H at 3.8 (singlet), 2 H at 4.8 (singlet), 1 H at 6.75 (singlet), 7 H from 7 to 8.3 (multiplet). 1 5 s Example 5 s 8-Bron\omethyl-6-methyl-2-phenyl-4H- (ll -ben2opyran-4-one (formula 4) Cl7H13Br02" MW : 329-20 0 f> Starting from 204 g (1.05 moles) of 1-(2-hydroxy-3- methoxymethyl-5-methylphenyl)ethanone and 210 g ^ (1.4 moles) of ethyl benzoate, after isolation the oil * obtained is treated with 520 ml of acetic acid and 410 ml of hydrobromic acid at 62 %. Weight obtained : 108g 10 (Rdt 31.2 »), PFk = 186°C (acetone), IR : Uc = 0 (pyrone) : 1640 cm~l . NMR (DMSO) <) in ppm with respect to the TMS, 3 H at 3.2 (singlet), 2 H at 5 (singlet), 1 H at 7 (singlet), 7 H from 7.3 to 8.3 (multiplet).
Example 6 : 15 8- Bromomethyl-2 - (2- thicnyl) -4H- til -benzopyran-4-one (formula 5) C14H9Br02 . MW = 321.2 Starting from 118 g (0.65 mole) of 1-(2-hydroxy-3-methoxymethylphenyl(ethanone and 127 (0.82 20 mole) of ethyl a-thenoate, the raw oil obtained is treated with 450 ml of hydrobromic acid at 62 % and 600 ml of acetic acid, according to example 4, 80.1 y (Rdt : 40 %) of a solid is obtained. PF : 174°C (ethanol).
IR : Uc = 0 (pyrone) : 160 cm"1 . NMR (CDCI3) in ppm 25 with respect to the TMS. 2 H at 4.8 (singlet), 1 H at 6.7 (singlet), 6 H from 7.1 to 8.3 (multiplet). 0 Example 7 : 8- Bromomethvl-2-(3-methoxvphenyl)-4H-I1]- benzopvran-4-one / 30 (formula 6) 7 C17H13Br03. MW = 3*55.20 Prepared according to example 2, starting from 57.1 q (0.38 mole) of 1-(3-methoxyphenyl)ethanone, and from 120 g (0.571 mole) of methyl 2-methoxy-3-methoxymethyl-5 benzoate. Weight obtained : 49.8 g (Rdt 38 %), PFjj = 160°C (toluene-hexane). IR : Uc = 0 = 1655 cm~^ . WMR (CDCI3), 3 H at 3.95, 2 H at 4.8 (singlet), 1 H at 6.8 (singlet), 6 H from 7.0 to 7.9 (multiplet), 1 H at 8.2 (pair of pair, = 8 Hz; J2 = 2 HZ). 1 o Example 8 : 8-Bromomethyl-3-methoxy-2-phenyl-4H-[ 1 ]-benzopyran-4-one (formula 7) C17H13Br03. MW = 345.20 IS A mixture of 11 g (0.041 mole) of 3-methoxy-8-methy1-2-phenyl-4H-[1]-benzopyran-4-one, 8.03 g (0.045 mole) of H-bromosucciniraide, 350 ml of carbon tetrachloride and 0.2 of azobis-isobutyronitrile is heated with reflux for 8 hours under ultraviolet radiation. It is filtered with heat, the filtrate is left overnight in the refrigerator. It is filtered, washed in water and recrystallised in ethyl acetate. Weight obtained : 6. 2g (Rdt : 43 ) . PFK = 157QC. IR : Uc = 0 : 1630 cm"1. NMR (CDC13) 3 H at 3.95 (singlet), 2 H at 4.83 2ri (singlet), 5 H from 7.2 to 7.9 (multiplet), 3 H from 8.1 to 3.5 (multiplet).
Example 9 : 8-Bromomethyl-6-methoxy-2-phenyl-4H-[1]-benzopyran-4-one (formula 8) 30 C17H13BrC>3. MW = 345.20 8 Prepared according to example 1 , starting from 1-(2-hydroxy-5-methoxy-3-methoxymethylphony1)-3-pheny1-1,3-propanedione. Weight obtained : 112.8 g (total Rdt : 60 S) . PFK = 1940c. ir ; l/c = 0 5 (pyrone) = 1650 cm"1 . NMR (DMSO), 3 H at 3.9 (singlet), 2 H at 5.1 (singlet), 8 H from 7.0 to 8.3 (multiplet). „ Example 10 : _ 8-Bromomethyl-2-(3,4-dimethoxypheny1)-4H- [1] - 0 10 benzopyran-4-one (formula 9) C18H15Br04. MW = 375.23 Prepared according to example 2, starting from 68.6 q (0.38 mole) of 1 -(3,4-dimethoxypheny1)ethanone and 15 120 g (0.571 mole) of methyl 2-methoxy-3-mcthoxy- methylbcnzoate. Weight obtained : 82 g (Rdt : 57 4).
PFk = 185°C (toluene-hexane). IR : Uc '= 0 (pyrone) = 1630 cm"1. NMR (CDCI3), 3 H at 3.97 (singlet), 3 H at 4.0 (singlet), 2 H at 4.8 (singlet), 1 H at 6.8 20 (singlet), 5 H from 6.9 to 7.9 (multiplet), 1 H at 8.22 (pair of pair, J-) = 8 Hz; J2 = 2 Hz).
Example 11 : 7,3-Diphenyl-8-methyl-4H-[1]-benzopyran-4-one (formula 10) 25 C22H16O2. MW = J12.37 A mixture of 98 g (0.433 mole) of 1 -(2-hydroxy-3-methyl-phenyl)-2-phenvlethanone, 98 g (0.433 mole) of benzoic acid anhydride and 62.4 g (0.433 mole) of sodium benzoate is heated for 7 hours at between 170 30 and 180°C. It is cooled, recovered with benzene, washed with water, then with an aqueous solution of | sodium bicarbonate, then with water. The benzene is evaporated under vacuum and the product obtained is recrystallised in toluene. Weight obtained : 36.4 g (Rdt : 27 §). PFk = 209-210°C. IR : Uc = 0 = 1630 cm-1. NMR (CDCI3) 3 H at 2.55 (singlet), 12 H from 7.1 to 7.7 (multiplet), 1 H at 0.15 (pair of pair, Ji = 8 Hz; J2 = 2 Hz).
Example 12 ; 8-Bromomethy1-2,3-diphenyl-4H-[1]-benzopyran-4-one (formula 11) C22H15Br02- MW = 391.27 Prepared accordinq to example 8, starting from 36 g (0.115 mole) of 2,3-diphenyl-8-methyl-4H-[11-bcnzopyran-4-ona. After filtration of the succinimide, the filtrate is evaporated under vacuum, the solid obtained is recovered with water and filtered. Weight obtained : 45 g (quantitative Rdt). PFj^ = 143-147°C. IR : VJc = 0 (pyrone) = 1635 cm-1. NMR (CDCI3) , 2 H at 4.8 (singlet), 12 H from 7 to 7.9 (multiplet), 1 H at 8.25 (pair of pair, J-| = 8 Hz; J 2 = 2Hz).
Example 1 3 : 8-Bromomethy1-2-(2-naphthyl)-4H-[1]-benzopyran-4-one (formula 12) c20H13Bl:03- MW = 362.22 Prepared according to example 2, starting from 105.1 g (0.5 mole) of methyl 2-methoxy-3-methoxymcthylbenzoate and 85.1 g (0.5 mole) of 1-(2-naphthyl)ethanone.
After isolation, the raw oil obtained is recovered with 600 ml of acetic acid and 426 ml of hydrobromic acid at 62 %.
By treatment according to the usual method, 61 g (Rdt : 30 %) PFq = 190-192°C (toluene) are obtained.
IR : Uc = 0 (pyrone) = 1650 cm"' .
Example 1 4 ; 8-Bromomethyl-2-(2-furyl) — 4H—{1]-benzopyran-4-one (formula 13) li Cj 4H9BCO3 . MW = 305.1 3 Prepared accordiny to example 2, startiny from 105.1 g (0 . *3 mole) of methyl 2-methoxy-3-methoxymcthylbcn'/.oato and 55 g (0.5 mole) of 1 - (2-furyl)ethanone. After being 5 isolated, the raw oil is recovered with 600 ml of acetic acid and 426 ml of hydrobromic acid at 62 %. By treatment according to the usual method, 23.4 y (Rdt : 15 %) are obtained. PFK = 210°C. IR : 1/c = O (pyrone) = 1660 cm-1. 10 Example 15 : 8-Bromomethyl-2-cyclohexyl-411-[1]-bcnzopyran-4-ono (formula 14) *-1 6^1 7®r®2 * ^ = 321.22 Prepared according to example 1, startiny from 18 q 1 5 (0.062 mole) of 1-cyclohexyl-3-(2-hydroxy-3-methoxymcthy 1 - phenyl)-1,3-propanedione. Weight obtained : 15.2 q (Rdt : 76 %). PFk = 130°C (acetone) - IR : c = 0 (pyrone) = 1645 cm"1. NMR (CDCI3) , 11 H from 1.1 to 3.0 (multiplet), 2 H at 4.7 (singlet), 1 H at 6.2 20 (singlet), 1 H at 7.3 (triplet, J = 8 Hz), 1 H at 7.65 (pair of pair, J-| = 8 Hz, J2 = 2H2) , 1 H at 8.15 (pair of pair, = 8 Hz, J2 = 2 Hz).
Example 16 : 8-Mcthy 1.-3-phenyl-4H-[1]-benzopyran-4-one 25 (formula 15) c16h12°2- mw = 236.27 A mixture of 85 y (0.375 mole) of 1 - (2-hydroxy-3-mothy1-phcnyl)-2-phenylethanone, 500 ml of pyridine, 50 ml of piperidine and 810 ml of triethyl orthoformate is 30 heated for 8 hours with reflux. It is then poured into a mixture of hydrochloric acid 6N and ice (3D. The precipitate obtained is filtered and recrystallised in isopropanol. Weight obtained : 80.9 g (Rdt : 91 %) , PFk = 110-111oc. IR : Uc = 0 = 1650 cin-1 . NMR (CDC13), 3 H at 2.5 (singlet), 7 II from 7.1 to 7.8 (multiplet), 1 H at 8.02 (sinylet), 1 H at 2.2 (pair o£ pair, J-| = 8 Hz, J2 = 2 Hz).
Example- 17 ; 8-Bromomothyl-3-phenyl-4H-[1]-benzopyran-4-onc (formula 16) C16HnBr02. MW - 315.17 Prepared according to example 8, starting from 80.9 g (0.34 mole) of 8-methyl-3-phenyl-4H-[1]-benzopyran-4-one and 73.4 g (0.41 mole) of N-bromosuccinimide. Weight obtained : 88.2 g (Rdt : 82 %). PFK = 142°C (ethyl acetate). IR : \/c : 0 (pyrone) = 1640 cm"'. NMR (CDCI3), 2 H at 4.8 (singlet), 7 H from 7.2 to 8.0 (multiplet), 1 H at 8.18 (singlet), 1 H at 8.4 (pair of pair, J-| = 8 Hz, J2 = 2 Hz).
Example 18 ; 8-Bromomethyl-2-methyl-4H-[1]-benzopyran-4-one (formula 17) CnH9Br02. MW = 253.10 Prepared according to example 1, starting from 27.4 g (0.116 mole) of 1 -(2-mcthoxy-3-mcthoxymethylphenyl)-1,3- butanedione• Weight obtained : 18 g (Rdt : 61 §).
PFK = 126-128°C (cyclohexane - ethyl acetate), IR : Ilc = 0 = 1670 cm"1. NMR (CDCI3), 3 H at 2.45 (ainglet), 2 H at 4.73 (singlet), 1 H at 6.27 (sinylet), 1 11 from 7.1 to 7.5 (multiplet), 1 H at 7.77 (pair of pair, J} = 8 Hz, J2 = 2 Hz), 1 H at 8.2 (pair of pair, J-) = 8 Hz, J 2 = 2 Hz).
Example 19 : 8-Bromomethyl-2-(phenyImethy1)-4H- [1]-benzopyran-4-one (formula 18) Ci7H13Br02. MW - 329.20 Prepared accordiny to example 1, startiny from n 1-(2-hydroxy-3-methoxymethylphenyl)-4-phcny]-1,3-butanedjone prepared in the previous example. Weight obtained : 47.5 g (Rdt : 72 %). PFK = 128°C (toluene-hexane). IR : (Jc = 0 (pyrone) = 1670 .
NMR (CDCI3), 2 H at 4 (singlet), 2 H at 4.63 (singlet) 1 H at 6.23 (singlet), 6 H from 7.1 to 7.55 (multiplet), 1 H at 7.7 (pair of pair, J-| = 8 Hz, = 2 Hz), 1 H at 8.2 (pair of pair, J-j = 8 Hz; J2 = 2 Hz) 13

Claims (8)

Claims
1. . 8-Bromoalkyl-4H-[1]-benzopyran-4-ones, characterised by the formula O :h2Bt where AR is a methyl, phenyl, methylphenyl, methoxyphenyl, dimethoxyphenyl, thienyl, furyl, naphthyl, cyclohexyl or benzyl radical, R-j is hydrogen, Y is hydrogen.
2. 8-Bromoalkyl-4H- [1]-benzopyran-4-ones , characterised by the formula where AR is a phenyl radical, Rj is hydrogen, Y is a methyl or methoxy radical.
3. . 8-Bromoalkyl-4H-[1]-benzopyran-4-ones, characterised by the formula I CH2Br II 0 where AR is a phenyl or hydrogen radical, R-j is a phenyl radical and Y is hydrogen. ^
4. Process for preparing 8-bromoalky1-4H-[1 ] -benzopyran-4-ones according to one of claims 1 to 3, (.. characterised by the ring closure of the 1,3-propanediones of the formula where AR, R^ and Y have the same meanings as 10 previously, R2 is hydrogen or a methyl radical, in the presence of hydrobromic acid.
5. Application of intermediate compounds according to one of claims 1 to 3 in the synthesis of pharmaceutical products and pesticides. 15
6. A compound in accordance with claim 1, as described in any one of the foregoing examples.
7. A process in accordance with claim 4, substantially as hereinbefore described in any one of the specific examples. 20
8. A compound in accordance with Claim 1, whenever prepared by the process claimed in Claim 4 or 7. F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.
IE2753/82A 1981-11-25 1982-11-18 8-haloalkyl-4h-(1)-benzopyran-4-ones and manufacturing procedures IE56916B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR8122019A FR2516921A1 (en) 1981-11-25 1981-11-25 HALOALKYL-8-4H- (1) BENZOPYRAN-4-ONES, AND METHODS OF PREPARATION

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IE822753L true IE822753L (en) 1983-05-25
IE56916B1 IE56916B1 (en) 1992-01-29

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EP (1) EP0080419B1 (en)
JP (1) JPS5896038A (en)
AR (1) AR243249A1 (en)
AT (1) ATE49760T1 (en)
AU (1) AU563066B2 (en)
CA (1) CA1197511A (en)
CS (1) CS236696B2 (en)
DD (1) DD204920A5 (en)
DE (1) DE3280092D1 (en)
DK (1) DK166778B1 (en)
ES (1) ES517636A0 (en)
FR (1) FR2516921A1 (en)
HU (1) HU194549B (en)
IE (1) IE56916B1 (en)
IL (1) IL67290A0 (en)
IN (1) IN158942B (en)
MA (1) MA19649A1 (en)
NO (1) NO162463C (en)
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OA (1) OA07256A (en)
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HU194549B (en) 1988-02-29
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IN158942B (en) 1987-02-21
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PT75885A (en) 1982-12-01
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ATE49760T1 (en) 1990-02-15

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