GB773468A - Process for the production of 3-substituted 4-hydroxy-coumarins - Google Patents
Process for the production of 3-substituted 4-hydroxy-coumarinsInfo
- Publication number
- GB773468A GB773468A GB23383/55A GB2338355A GB773468A GB 773468 A GB773468 A GB 773468A GB 23383/55 A GB23383/55 A GB 23383/55A GB 2338355 A GB2338355 A GB 2338355A GB 773468 A GB773468 A GB 773468A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ester
- malonic acid
- benzyl
- aryl
- heated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 3-substituted 4-hydroxy-coumarins Chemical class 0.000 title abstract 7
- 238000000034 method Methods 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 8
- 125000003118 aryl group Chemical group 0.000 abstract 5
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 2
- 125000005418 aryl aryl group Chemical group 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical group 0.000 abstract 2
- YVWCGEMMBLBBOC-UHFFFAOYSA-N 2-[(2-methylphenyl)methyl]propanedioic acid Chemical compound CC1=CC=CC=C1CC(C(O)=O)C(O)=O YVWCGEMMBLBBOC-UHFFFAOYSA-N 0.000 abstract 1
- VBTZGWPXLRROLN-UHFFFAOYSA-N 3,6-dibenzyl-4-hydroxychromen-2-one Chemical compound C(C1=CC=CC=C1)C=1C(OC2=CC=C(C=C2C1O)CC1=CC=CC=C1)=O VBTZGWPXLRROLN-UHFFFAOYSA-N 0.000 abstract 1
- PNKUXTBURQJLJF-UHFFFAOYSA-N 3,8-dibenzyl-6-chloro-4-hydroxychromen-2-one Chemical compound C(C1=CC=CC=C1)C=1C(OC2=C(C=C(C=C2C1O)Cl)CC1=CC=CC=C1)=O PNKUXTBURQJLJF-UHFFFAOYSA-N 0.000 abstract 1
- XXCCGMGKPAOLDF-UHFFFAOYSA-N 3-benzyl-4-hydroxy-6-phenylchromen-2-one Chemical compound C(C1=CC=CC=C1)C=1C(OC2=CC=C(C=C2C1O)C1=CC=CC=C1)=O XXCCGMGKPAOLDF-UHFFFAOYSA-N 0.000 abstract 1
- AEIVRFFWQSJCAR-UHFFFAOYSA-N 3-benzyl-4-hydroxychromen-2-one Chemical compound O=C1OC=2C=CC=CC=2C(O)=C1CC1=CC=CC=C1 AEIVRFFWQSJCAR-UHFFFAOYSA-N 0.000 abstract 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 abstract 1
- ROQRPLOBMXNEKR-UHFFFAOYSA-N 4-hydroxy-3-(3-methylbutyl)chromen-2-one Chemical compound C(CC(C)C)C=1C(OC2=CC=CC=C2C1O)=O ROQRPLOBMXNEKR-UHFFFAOYSA-N 0.000 abstract 1
- VXIXUWQIVKSKSA-UHFFFAOYSA-N 4-hydroxycoumarin Chemical class C1=CC=CC2=C1OC(=O)C=C2O VXIXUWQIVKSKSA-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 abstract 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 abstract 1
- XSVCANCIANAGQH-UHFFFAOYSA-N bis(2-benzyl-4-chlorophenyl) 2-benzylpropanedioate Chemical compound C(C1=CC=CC=C1)C1=C(C=CC(=C1)Cl)OC(C(C(=O)OC1=C(C=C(C=C1)Cl)CC1=CC=CC=C1)CC1=CC=CC=C1)=O XSVCANCIANAGQH-UHFFFAOYSA-N 0.000 abstract 1
- DRMGEGROCCTZCP-UHFFFAOYSA-N bis(4-benzylphenyl) 2-benzylpropanedioate Chemical compound O=C(OC1=CC=C(CC2=CC=CC=C2)C=C1)C(CC1=CC=CC=C1)C(=O)OC1=CC=C(CC2=CC=CC=C2)C=C1 DRMGEGROCCTZCP-UHFFFAOYSA-N 0.000 abstract 1
- TZQQBRNYMPYQAN-UHFFFAOYSA-N bis(4-methylphenyl) 2-[(4-chlorophenyl)methyl]propanedioate Chemical compound C1(=CC=C(C=C1)C)OC(C(C(=O)OC1=CC=C(C=C1)C)CC1=CC=C(C=C1)Cl)=O TZQQBRNYMPYQAN-UHFFFAOYSA-N 0.000 abstract 1
- VKKQMGNVKNCTLQ-UHFFFAOYSA-N bis(4-phenylphenyl) 2-benzylpropanedioate Chemical compound C1(=CC=CC=C1)C1=CC=C(C=C1)OC(C(C(=O)OC1=CC=C(C=C1)C1=CC=CC=C1)CC1=CC=CC=C1)=O VKKQMGNVKNCTLQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009835 boiling Methods 0.000 abstract 1
- YFDSAMDKMHIOSI-UHFFFAOYSA-N diphenyl 2-(3-methylbutyl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)CCC(C)C)=O YFDSAMDKMHIOSI-UHFFFAOYSA-N 0.000 abstract 1
- HSOYWJFSKNKDDP-UHFFFAOYSA-N diphenyl 2-(4-benzyl-3H-dithiol-3-yl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)C1SSC=C1CC1=CC=CC=C1)=O HSOYWJFSKNKDDP-UHFFFAOYSA-N 0.000 abstract 1
- ZFHMYYUMUWWGAG-UHFFFAOYSA-N diphenyl 2-(4-bromophenyl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)C1=CC=C(C=C1)Br)=O ZFHMYYUMUWWGAG-UHFFFAOYSA-N 0.000 abstract 1
- KXDSIYCPLIEAJS-UHFFFAOYSA-N diphenyl 2-(4-methoxyphenyl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)C1=CC=C(C=C1)OC)=O KXDSIYCPLIEAJS-UHFFFAOYSA-N 0.000 abstract 1
- RSCCYVABAVRIHV-UHFFFAOYSA-N diphenyl 2-(4-propan-2-ylphenyl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)C1=CC=C(C=C1)C(C)C)=O RSCCYVABAVRIHV-UHFFFAOYSA-N 0.000 abstract 1
- IWAVDMLFZWGGFB-UHFFFAOYSA-N diphenyl 2-[(3,4-dimethoxyphenyl)methyl]propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)CC1=CC(=C(C=C1)OC)OC)=O IWAVDMLFZWGGFB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 235000013580 sausages Nutrition 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000001256 steam distillation Methods 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
Classifications
-
- 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
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
4-Hydroxycoumarins and their 1-thio analogues of the general formula: <FORM:0773468/IV(b)/1> (wherein X is O or S, R is alkyl, alkoxyalkyl, aryloxyalkyl, aryl or alkylmercaptoalkyl, aralkyl, aryl, arylaryl, or aralkylaryl wherein aromatic nuclei can be substituted by halogen, alkyl, alkoxy or nitro groups, and Ar is o-arylene aryl-o-arylene or aralkyl-o-arylene wherein aromatic nuclei can be substituted by halogen, alkyl or alkoxy groups) are prepared by heating to at least 240 DEG C., preferably 300 DEG C., a -substituted malonic acid diaryl esters of formula Ar1XCOCHRCOXAr1, wherein Ar1 represents the aryl, arylaryl or aralkylaryl radical corresponding to Ar, having a hydrogen atom in at least one o-position with regard to X. In examples: (1) isoamyl malonic acid diphenyl ester is heated 90 minutes at 300 DEG C. in a flask fitted with a wide sloping tube, phenol distils off, the residue is extracted with sodium hydroxide solution and 3-isoamyl-4-hydroxycoumarin precipitated with HCl; similarly prepared are 3 - methyl -, ethyl -, n - propyl -, isopropyl -, n - butyl -, n - amyl -, isoamyl, n-hexyl -, phenyl -, and benzyl - 4 - hydroxycoumarin; (2) benzylmalonic acid bis-(p-benzylphenyl) ester is heated in a sausage flask, and then 4-benzylphenol distilled off under reduced pressure, leaving 3,6 - dibenzyl - 4 - hydroxycoumarin; (3) benzylmalonic acid bis-(p-phenylphenyl) ester is heated at 300 DEG C., and p-phenylphenol removed by steam distillation, yielding 3-benzyl-4-hydroxy-6-phenylcoumarin; (4) benzylmalonic acid bis-(o-benzyl-p-chlorophenyl) ester is heated as above and 3,8-dibenzyl - 4 - hydroxy - 6 - chlorocoumarin isolated by extraction with boiling aqueous caustic soda lye, filtration and acidification. Other starting materials specified for the cyclisation process are benzyl dithiolmalonic acid diphenyl ester, 4-chlorobenzyl malonic acid bis-p-cresyl ester, 2-methyl-benzyl malonic acid bis-4-methoxyphenyl ester, 3,4-dimethoxy-benzyl malonic acid diphenyl ester, 4-bromophenyl malonic acid diphenyl ester, 4-isopropylphenyl malonic acid diphenyl ester and 4-methoxyphenyl malonic acid diphenyl ester.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH773468X | 1954-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB773468A true GB773468A (en) | 1957-04-24 |
Family
ID=4535611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB23383/55A Expired GB773468A (en) | 1954-08-17 | 1955-08-15 | Process for the production of 3-substituted 4-hydroxy-coumarins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB773468A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3022317A (en) * | 1956-01-20 | 1962-02-20 | Geigy Chem Corp | 3-benzyl-4-hydroxycoumarin and a process for the preparation of derivatives of 3-benzyl-4-hydroxycoumarin |
-
1955
- 1955-08-15 GB GB23383/55A patent/GB773468A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3022317A (en) * | 1956-01-20 | 1962-02-20 | Geigy Chem Corp | 3-benzyl-4-hydroxycoumarin and a process for the preparation of derivatives of 3-benzyl-4-hydroxycoumarin |
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