IE56916B1 - 8-haloalkyl-4h-(1)-benzopyran-4-ones and manufacturing procedures - Google Patents

8-haloalkyl-4h-(1)-benzopyran-4-ones and manufacturing procedures

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IE56916B1
IE56916B1 IE2753/82A IE275382A IE56916B1 IE 56916 B1 IE56916 B1 IE 56916B1 IE 2753/82 A IE2753/82 A IE 2753/82A IE 275382 A IE275382 A IE 275382A IE 56916 B1 IE56916 B1 IE 56916B1
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benzopyran
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singlet
ones
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Lipha
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    • 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
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    • C07—ORGANIC CHEMISTRY
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    • 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
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    • 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
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    • 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
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    • 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

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

L'invention concerne des haloalkyl -8-4H-[1]-benzo- pyran-4-ones. Les composés sont représentés par la formule dans laquelle AR est l'hydrogène, un radical phényle, phényle substitué - par un radical alkyle inférieur, alkoxy inférieur ou un halogène - un radical thényle, pyridyle, furyle, naphtyie, alkyle, cycloalkyle ou aralkyle, X est un halogène et Y l'hydrogène, un radical alkyle inférieur, alkoxy ou un halogène, R1 est l'hydrogène, un radical alkoxy ou phényle. Ils sont utilisables en tant que produits industriels intermédiaires dans la synthèse de produits pharmaceutiques et de pesticides.

Description

Z The present invention concerns 8-haLoalky]-411[1]-benzopyran-4-ones and the preparation thereof. 8-Haloalkyl-4H-[1]-benzopyran-4-ones are represented by the formula CEzBr where AR is a methyl, phenyl, methyIphenyl, methoxyphenyl, dimethoxyphenyl, thienyl, furyl, naphthyl, cyclohexyl or benzyl radical, Y is hydrogen, Rj is hydrogen.
They are also represented by the said formula I, where AR is a phenyl radical, Rj is hydrogen, Y is a methyl or methoxy radical.
They are also represented by the same formula I, where AR is hydrogen or a phenyl radical, R-, is a .15 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-ΟΧΟ-4Π-1 lJ-benzopyran-8-yl] alkanoic acids and their derivatives which are the subject matter of European Patent Application No. 80.934. 8-Bromoalky1-4H- [1]benzopyran-4-ones constitute a particularly interesting class.
Bromobenzopyranones corresponding to formula I can be prepared, with good yields, by ring closure of the <2 1,3-propanediones of the formula j where AR, R-j and Y have the same meanings as previously, 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 : 8-Bromomethyl-2-phcny1-4B-[1J-bcnzopyran-4-one (formula 1) C^H^BrO^ MW = 315.17 A mixture of 361 g (1.40 moles) of 1-(2-hydroxy-3-methoxy methylphcnyl)-3-phenyl-l,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 %) of a white solid are obtained. PF : 182-183°C. IR : Oc - 0 : 1650 cm1 . NMR (DMSO) Analysis : C % H % Br $ Calculated 60.98 3.51 25.36 Found 61 .12 3.35 25.34 Example 2 : 8-Bromoroethy1-2-pheny1-4H-[1] -benzopyran-4-one ( formula 1) Cl6HnBrO2. MW = 315.17 880 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 a (1,32 moles) of methyl 3-methoxymethyl-2-methoxybenzoate and 105.7 g (0.88 mole) of acetophenone IO 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 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 formed is filtered, washed in water and recrystallised in acetone. Weight obtained : 123 g (Rdt : 51.3 %), PFG : 1 82-183°C.
Example 3 : 8-8romomethyl-2-(4-methylphenvl ) -4H-[1]-benzopvran-430 one (formula 2) C17H13BrO2. MW : 329.20 Prepared according to example 2, starting from 51.1 g (0.38 mole) of 1-(4-methylphenyl) ethanone, 120g (0.571 mole) of methyl 2-methoxy-3-methoxymethy1δ benzoate. After isolation, the oil obtained is recovered with 348 ml of acetic acid and 348 ml of hydrobromic acid et 62 Weiyht obtained : 53-3 (Rdt : 41.8 §), PF^ : 191°C (toluene), IR : V) c = 0 (pyrone) : 1640 cm-1. NMR (DMSO) d in ppm with respect to the TMS, 3 H at 2-4 (singlet), 2 H at 5-1 (singlet), 1 H at 7 (singlet), 7 H from 7.3 to 8.3 (multiplet).
Example 4 : 8-Bromomethy1-2-(4-methoxyphenyl)-4H- (ll -benzopvran-410 one (formula 3) C17H13BrO3. MW = 345.20 Prepared according to example 2, starting from 57. L4 g (0.38 mole) of 1-(4-methoxyphenyl)ethanonc, 120g (0.571 mole) of methyl 2-methoxy-3-iuothoxyniethylbenzoate. 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 : U c = 0 (pyrone) ; 1640 cm1. 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).
Example 5 5 8-ΒΓθπιοπίθΐ.Ην1-6~ϊηβ1·ΐγ/1-2-ρΗθηγ1-4Η- (ll -ben2opyran-4-one (formula 4) Cl7H13Br°2* MW : 329·20 Starting from 204 g (1.05 moles) of 1-(2-hydroxy-3methoxymethyl-5-methy Iphenyl) ethanonc 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 (Rdt 31.2 M, PFK = 186°C (acetone), IR : Oc = 0 (pyrone) : 1640 cm'b NMR (DMSO) J 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 : 8-Bromomethyl-2- (2-thienyl) -4H-Jl) -benzopyran-4-one (formula 5) C..HQBr02 . MW = 321.2 14 9 z Starting from 118 g (0.65 mole) of 1-(2-hydroxy-3me thoxyme thy lpheny Dcthanone and 127 g (0.82 mole) of ethyl α-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 g (Rdt ; 40 %) of a solid is obtained. PF : 174°C (ethanol).
IR : Vc = 0 (pyrone) : 1640 cn\ NMR (CDCI3) in ppm 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).
Example 7 : 8- Bromomethyl-2-(3-methoxyphenyl)-4H-I1]benzopyran-4-one (formula 6) C17Hi3Br03· MW = 345.20 Prepared according to example 2, starting from 57.1 g (0.38 mole) of 1-(3-methoxyphenyl)ethanone, and from 120 g (0.571 mole) of methyl 2-methoxy-3"methoxymethyl5 benzoate. Weight obtained : 49.8 g (Rdt 38 %), PFK s 160°C (toluene-hexane). IR : Uc = 0 = 1655 cm-^. NMR (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, J-j = 8 Hz; J2 = 2 HZ).
Example 8 : 8-Bromomethyl"3-methoxy-2-phenyl-4H-[1]ben2Qpyran-4-one (formula 7) Cl?H13BrO3. MW = 345.20 A mixture of 11 g (0.041 mole) of 3-methoxy-8-methyl-2phenyl-4H-[11-benzopyran-4-one, 8.03 g (0.045 mole) of N-bromosuccinimide, 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 = 157«C. IR : Uc = 0 : 1630 cm1. NMR (CDC13) 3 H at 3.95 (singlet), 2 H at 4.83 (singlet), 5 H from 7.2 to 7.9 (multiplet), 3 H from 8.1 to 3.5 (multiplet). a Example 9 : 8-Bromomethyl-6-methoxy-2-phenyl-4H-[1]-benzopyran-4-one (formula 8) C17H13Br°3* MV/ = 345.20 Prepared according to example 1, starting from 1-(2-hydroxy-5-methoxy-3-methoxymethyIphenyl)-3pheny1-1,3-propanedione. Weight obtained : 112.8 g (total Rdt : 60 3). PFK = 194°c. ir ; Uc = 0 (pyrone) = 1650 cm1 . NMR (DMSO), 3 H at 3.9 (singlet), 2 H at 5=1 (singlet), 8 H from 7.0 to 8.3 (multiplet). μ Example 10 : 8-Bromomethyl-2-(3,4-dimethoxyphenyi)-4H- [1] - p benzopyran-4-one (formula 9) C18H15BrO4. MW = 375.23 Prepared according to example 2, starting from 68.6 g (0.38 mole) of 1-(3,4-dimethoxyphcnyl)ethanone and 120 g (0.571 mole) of methyl 2-methoxy-3-mcthoxymethylbenzoate. Weight obtained : 82 g (Rdt : 57¾).
PFk = 185°C (toluene-hexane). IR : U c '= 0 (pyrone) = 1630 cm1. 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 (singlet), 5 H from 6.9 to 7.9 (multiplet), 1 H at 8.22 (pair of pair, = 8 Hz; J2 = 2 Hz).
Example 11 ; 2,3-Diphenyl-8-methy1-4H-[1]-benzopyran-4-one (formula 10) C22h16°2- MW = 312.37 A mixture of 98 g (0.,433 mole) of 1-(2-hydroxy-3-methylphenyl)-2-phcnvlethanone, 98 g (0.433 mole) of benzoic acid anhydride and 62.4 g (0.433 mole) of φ sodium benzoate is heated for 7 hours at between 170 and 180°C. It is cooled, recovered with benzene, washed with water, then with an agueous 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 S). PFK = 209-210°C. IR : Uc = 0 = 1630 cm-'. NMR (CDCI3) 3 H at 2.55 (singlet), 12 H from 7.1 to 7.7 (multiplet), 1 H at 8.15 (pair of pair, J] = 8 Hz; J2 - 2 Hz).
Example 12 ; 8-Bromomethy1-2,3-diphenvl-4H-[1]-benzopyran-4-one (formula 11) C22H15BrO2- MW = 391.27 Prepared according to example 8, starting from 36 g (0.115 mole) of 2,3-diphenyl-8-methyl-4H-[1]bcnzopyran-4-one. 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). PFg = 143-147°C. IR : Uc = 0 (pyrone) = 1 635 cm-'. NMR (CDCI3), 2 H at 4.8 (singlet), 12 H from 7 to 7.9 (multiplet), 1 H at 8.25 (pair of pair, = 8 Hz; = 2Ηζϋ· Example 13 ; 8-Bromomethy1-2-(2-naphthyl)-4H-[1]-benzOpyran-4-one (formula 12) c20h13Bl'°3- MW = 362.22 Prepared according to example 2, starting from 105.1 g (0.5 mole) of methyl 2-methoxy-3-methoxymethylbenzoate 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'.
I Example 1 4 ; 8-Bromomethyl-2-(2-furyl) -4H-{ 1]-benzopyran-4-one (formula 13) 1® C^HgBrO^. MW = 305.1 3 Prepared according to example 2, starting from 105.1 g (0.5 mole) of methyl 2-methoxy-3-met.hoxymcthylbcn'zoate □ nd 55 g (0.5 mole) of 1 - (2-furyl)ethanone. After being 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 g (Rdt : 15%) are obtained. PFK = 210°C. IR : U c = O (pyrone) = 1660 on1.
Example 15 : 8-Bromomethyl-2-cyclohexyl-411-[1)-bcnzopyran-4-one (formula 14) c16ti17Br®2· Mw ~ 321.22 Prepared according to example 1, startiny from 18 g (0.062 mole) of 1-eyelohexy1-3-(2-hydroxy-3-methoxymethyl pheny1)-1,3-propanedione. Weight obtained : 15.2 q (Rdt : 76 %). PFK χ 130°C (acetone) - IR : Vc = 0 (pyrone) = 1645 on1 . NMR (CDCI3), 11 H from 1.1 to 3.0 (multiplet), 2 H at 4.7 (singlet), 1 H at 6.2 (singlet), 1 H at 7.3 (triplet, J = 8 Hz), 1 H at 7.65 (pair of pair, = 8 Hz, J2 = 2H2), 1 H at 8.15 (pair of pair, = 8 Hz, J2 = 2 Hz).
Example 16 ; 8-Mcthy1-3-phenvl-4H-[1]-benzopyran-4-one ( formula 15) C16H12°2- MW = 236.27 A mixture of 85 g (0.375 mole) of 1 - (2-hydroxy-3-mothy1phenyl)-2-phenylcthanone, 500 ml of pyridine, 50 ml of piperidine and 810 ml of triethyl orthoformate is heated for 8 hours with reflux. It is then poured into a mixture of hydrochloric acid 6N and ice (31*) . The precipitate obtained is filtered and recrystallised in isopropanol. Weight obtained : 80.9 g (Rdt : 91 %), PFK = 110-111oc. ir : Oc = 0 = 1650 cm-1 . NMR (CDClg), 3 H at 2.5 (singlet), 7 H from 7.1 to 7.8 (multiplet), 1 H at 8.02 (singlet), 1 H at 2.2 (pair of pair, J-| = 8 Hz, J2 - 2 Hz).
Example 17 : 8-Bromomcthyl-3-phenyl-4H-[1]-benzopyran-4-onc (formula 16) m C16H11BrO2. 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 v and 73*4 g (0.41 mole) of N-bromosuccinimide. Weight obtained : 88.2 g (Rdt : 82 %). PFK = 142°C (ethyl acetate). IR : Vc : 0 (pyrone) = 1640 cm’', NMR (CDC13), 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, = 8 Hz, J2 = 2 Hz).
Example 18 ; 8-Bromomethyl-2-methyl-4H-[1]-benzopyran-4-one (formula 17) CnH9BrO2. MW = 253.10 Prepared according to example 1, starting from 27.4 g (0.116 mole) of 1 -(2-mcthoxy-3-mcthoxymethylphenyl)-1,3butanedione · Weight obtained : 18 g (Rdt : 61 %)PFK = 126-128°C (cyclohexane - ethyl acetate), IR : Vc = 0 = 1670 cm-1. NMR (CDCI3), 3 H at 2.45 (singlet), 2 H at 4.73 (singlet), 1 H at 6.27 (singlet), 1 H from 7.1 to 7.5 (multiplet), 1 H at 7.77 (pair of pair, Jj = Hz, J2= 2 Hz), 1 H at 8.2 (pair of pair, = 8 Hz, J2 = 2 Hz).
Example 19 : 8-Bromomethy1-2-(phenylmethyl)-4H- [1]-benzopyran-4-onc (formula 18) c17Hi3BrO2. MW - 329.20 Prepared according to example 1, starting from 1-(2-hydroxy-3-methoxymethylphenyl)-4-phcny]-1,3butanedjone prepared in the previous example. Weight obtained : 47.5 g (Rdt : 72 %). PFK = 128°C (toluene-hexane). IR : |jc = 0 (pyrone) = 1670 cm~1 .
NMR (CDCl^), 2 H at 4 (singlet), 2 H at 4.63 (singlet), H at 6.23 (singlet), 6 H from 7.1 to 7.55 (multiplet), 1 H at 7.7 (pair of pair, J-j = 8 Hz, J2 = Hz), 1 H at 8.2 (pair of pair, J-j = 8 H2; J2 = 2 Hz).

Claims (7)

1.Claims Ί . 8-Bromoalkyl-4H-[1]-benzopyran-4-ones, characterised by the formula 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 CK 2 Br where AR is a phenyl radical, is hydrogen, Y is a methyl or methoxy radical.
3. . 8-Bromoalkyl-4H-[1]-benzopyran-4-ones, characterised by the formula ίί where AR is a phenyl or hydrogen radical, R 1 i s 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 1,3propanediones of the formula where AR, R^ and Y have the same meanings as 10 previously, R2 *- s hydrogen or a methyl radical, in the presence of hydrobromic ac.id.
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, asdescribed 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.
IE2753/82A 1981-11-25 1982-11-18 8-haloalkyl-4h-(1)-benzopyran-4-ones and manufacturing procedures IE56916B1 (en)

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FR8122019A FR2516921A1 (en) 1981-11-25 1981-11-25 HALOALKYL-8-4H- (1) BENZOPYRAN-4-ONES, AND METHODS OF PREPARATION

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IE56916B1 true IE56916B1 (en) 1992-01-29

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