GB683344A - Process of making substituted 4-methyl coumarins - Google Patents

Process of making substituted 4-methyl coumarins

Info

Publication number
GB683344A
GB683344A GB28849/50A GB2884950A GB683344A GB 683344 A GB683344 A GB 683344A GB 28849/50 A GB28849/50 A GB 28849/50A GB 2884950 A GB2884950 A GB 2884950A GB 683344 A GB683344 A GB 683344A
Authority
GB
United Kingdom
Prior art keywords
diketene
run
condensing agent
fused
phenol
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
Application number
GB28849/50A
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.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of GB683344A publication Critical patent/GB683344A/en
Expired legal-status Critical Current

Links

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
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • 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
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • 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
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

4-Methylcoumarins, containing a substituent in the benzene nucleus or having a further ring fused thereto, are manufactured by the action of a dehydrating condensing agent on an acetoacetic ester of the general formula <FORM:0683344/IV (b)/1> (wherein R represents one or more substituents or a fused-on ring) obtainable by reacting the corresponding phenol with an equimolecular proportion of diketene in the presence of an esterification catalyst at an elevated temperature not substantially above the melting point of the phenol. Suitable starting materials (which need not be isolated in the pure state) are the acetoacetates of the phenol homologues (e.g. cresols and xylenols) and the naphthols, and the mono-acetoacetates of polyhydric phenols. The condensation is advantageously effected by running the acetoacetate into the condensing agent at a temperature between 0 DEG and about 50 DEG C. In examples: (1) resorcinol is fused with a small amount of pyridine and an equimolecular proportion of diketene is run in, and the resulting monoacetoacetate is run into 78 per cent sulphuric acid, producing methyl umbelliferone; (2) pyrogallol similarly yields 7 : 8-dihydroxy-4-methylcoumarin; (3) 6-hydroxy-4-methylcoumarin is similarly prepared from hydroquinone, except that the first step is carried out in benzene solution; (4) a -naphthol is treated as in (1) to produce 4-methyl-1 : 2-a -naphthopyrone; (5) diketene is run in a slow jet into a heated mixture of p-cresol with a trace of dimethylaniline, and the resulting acetoacetate is treated as in (2) to form 4 : 6-dimethylcoumarin; (6) resorcinol is reacted with diketene in the presence of triethylamine and the product is run into concentrated phosphoric acid, producing methylumbelliferone. Zinc chloride is additionally specified as a condensing agent, and sodium acetate, benzenesulphonic acid and concentrated sulphuric acid as esterification catalysts.
GB28849/50A 1949-11-25 1950-11-24 Process of making substituted 4-methyl coumarins Expired GB683344A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR683344X 1949-11-25

Publications (1)

Publication Number Publication Date
GB683344A true GB683344A (en) 1952-11-26

Family

ID=9023835

Family Applications (1)

Application Number Title Priority Date Filing Date
GB28849/50A Expired GB683344A (en) 1949-11-25 1950-11-24 Process of making substituted 4-methyl coumarins

Country Status (1)

Country Link
GB (1) GB683344A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5231194A (en) * 1989-12-21 1993-07-27 Sumitomo Chemical Co., Ltd. Process for producing coumarin derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5231194A (en) * 1989-12-21 1993-07-27 Sumitomo Chemical Co., Ltd. Process for producing coumarin derivatives

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