IE45643B1 - Process for the preparation of 6,6'-oxy bis (4-halo-2h-pyran-3(6h)-ones) and their use in preparing gamma-pyrones - Google Patents

Process for the preparation of 6,6'-oxy bis (4-halo-2h-pyran-3(6h)-ones) and their use in preparing gamma-pyrones

Info

Publication number
IE45643B1
IE45643B1 IE585/79A IE58579A IE45643B1 IE 45643 B1 IE45643 B1 IE 45643B1 IE 585/79 A IE585/79 A IE 585/79A IE 58579 A IE58579 A IE 58579A IE 45643 B1 IE45643 B1 IE 45643B1
Authority
IE
Ireland
Prior art keywords
pyrones
pyran
gamma
formula
compound
Prior art date
Application number
IE585/79A
Other versions
IE790585L (en
Original Assignee
Pfizer
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
Priority claimed from US05/721,885 external-priority patent/US4082717A/en
Application filed by Pfizer filed Critical Pfizer
Publication of IE790585L publication Critical patent/IE790585L/en
Publication of IE45643B1 publication Critical patent/IE45643B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Pyrane Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Cosmetics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Furan Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Transforming Electric Information Into Light Information (AREA)
  • Picture Signal Circuits (AREA)
  • Processing Of Color Television Signals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Seasonings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

The gamma-pyrones of formula I in which the symbols have the meaning given in Claim 1 are obtained by a simple and economic "one-pot" process by reaction of a furfuryl alcohol of formula III with at least 2 equivalents of a halogenated oxidising agent, in aqueous solution at a temperature of between -50 DEG and +50 DEG C, and then the reaction mixture is heated until hydrolysis of the intermediate formed is virtually complete. The gamma-pyrones obtained can be used as products which enhance flavour and fragrance in food and cosmetic preparations.

Description

This invention relates to novel 6,6'-oxy bis[4-halo2H-pyran-3(6H)-ones] , a process for their production and a process for their further conversation to gamma-pyrones, particularly to maltol (3-hydroxy-2-mathyl-4H-pyran~4-one) and related compounds.
Thus according to the invention there are provided novel compounds of the general formula: wherein R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl 10 or benzyl; and X is chlorine or bromine.
Such dimers are prepared by dehydration of a 4-halodihydropyran of the general formula: (II) I 3 6 4 3 where R and X are as defined above, by heating under vacuum. 4-Halo-dihydropyrans of formula (II) are described and claimed in Patent Specification No. 45644 of even date.
Hydrolysis of the 6,6'-oxybis[4-halogeno-2H-pyran-3(6H)5 one] of formula (I), by heating an aqueous solution until hydrolysis is substantially complete yields a gamma-pyrone of the formula: where R is as previously defined.
The preparation of the novel compounds of the invention and their conversion to gamma-pyrones is illustrated by the following Examples.
Example 1 4-Bromo-6-hydroxy-2-methyl-2H-pyran-3(6H)-one was heated under vacuum for 16 hours at 40°C. The resulting oily solid was crystallised from isopropyl alcohol to yield 6,6'-oxybis [4-bromo-2-methyl-2H-pyran-3(6H)-one] , mp 125°C.
Example 2 The method of Example 1 may be repeated starting with a compound of the formula to yield a compound of the formula wherein R is hydrogen, ethyl, propyl, butyl, phenyl or 5 benzyl; X is bromine or chlorine.
R X M.P. (°C.) CH3 Cl 177-179 CH2CH3 Cl 132-135 Example 3 a compound of the formula wherein R is hydrogen, methyl, ethyl, propyl, butyl, phenyl 3 6 4 3 - 5 or benzyl and X is bromine or chlorine is refluxed for about 5 hours in 35% phosphoric acid to yield a compound of the formula R wherein R is as defined above. - 6 ZJ i) Ο ‘, υ

Claims (4)

1. CIAIMS;1. A compound of the general formula wherein R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl 5 or benzyl; and X is chlorine or bromine.
2. A process for preparing a compound of the general formula wherein R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl 10 or benzyl; X is chlorine or bromine which comprises dehydrating under vacuum a compound of the general formula - 7 45643
3. A process for preparing a gamma-pyrone of the general formula which comprises heating in aqueous solution at 70-160°C 5 until hydrolysis is substantially complete a compound of the formula wherein R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or benzyl and X is chlorine or bromine. 10
4. A process as claimed in claim 2 or 3 substantially as hereinbefore described with reference to the Examples.
IE585/79A 1976-08-02 1977-07-29 Process for the preparation of 6,6'-oxy bis (4-halo-2h-pyran-3(6h)-ones) and their use in preparing gamma-pyrones IE45643B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US71090176A 1976-08-02 1976-08-02
US05/721,885 US4082717A (en) 1976-08-02 1976-09-09 Preparation of gamma-pyrones
IE1587/77A IE45641B1 (en) 1976-08-02 1977-07-29 Process for the preparation of gamma-pyrones

Publications (2)

Publication Number Publication Date
IE790585L IE790585L (en) 1978-02-02
IE45643B1 true IE45643B1 (en) 1982-10-20

Family

ID=27108548

Family Applications (5)

Application Number Title Priority Date Filing Date
IE585/79A IE45643B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 6,6'-oxy bis (4-halo-2h-pyran-3(6h)-ones) and their use in preparing gamma-pyrones
IE587/79A IE45645B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 6-alkoxy and 6-acyloxy-4-halo-2h-pyrones and their use in the synthesis of gamma-pyrones
IE586/79A IE45644B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 4-halo-6-hydroxy-2h-pyran-3(6h)-ones and their use in the synthesis of gamma-pyrones
IE584/79A IE45642B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 6-hydroxy-2h-pyran-3(6h)-ones useful in the synthesis of gamma-pyrones
IE1587/77A IE45641B1 (en) 1976-08-02 1977-07-29 Process for the preparation of gamma-pyrones

Family Applications After (4)

Application Number Title Priority Date Filing Date
IE587/79A IE45645B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 6-alkoxy and 6-acyloxy-4-halo-2h-pyrones and their use in the synthesis of gamma-pyrones
IE586/79A IE45644B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 4-halo-6-hydroxy-2h-pyran-3(6h)-ones and their use in the synthesis of gamma-pyrones
IE584/79A IE45642B1 (en) 1976-08-02 1977-07-29 Process for the preparation of 6-hydroxy-2h-pyran-3(6h)-ones useful in the synthesis of gamma-pyrones
IE1587/77A IE45641B1 (en) 1976-08-02 1977-07-29 Process for the preparation of gamma-pyrones

Country Status (36)

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JP (7) JPS5318578A (en)
AR (1) AR216080A1 (en)
AT (3) AT362790B (en)
BE (1) BE855965A (en)
BG (4) BG28989A4 (en)
BR (1) BR7703970A (en)
CA (3) CA1095921A (en)
CH (4) CH625798A5 (en)
CS (3) CS203921B2 (en)
DD (1) DD132494A5 (en)
DE (3) DE2728499C2 (en)
DK (4) DK153483C (en)
EG (1) EG13080A (en)
ES (5) ES459994A1 (en)
FI (6) FI72722C (en)
FR (1) FR2372821A1 (en)
GB (5) GB1538375A (en)
GR (1) GR68938B (en)
HK (5) HK30481A (en)
HU (4) HU185687B (en)
IE (5) IE45643B1 (en)
IT (1) IT1106258B (en)
LU (1) LU77600A1 (en)
MX (1) MX4597E (en)
MY (3) MY8100267A (en)
NL (5) NL170955C (en)
NO (7) NO150561C (en)
NZ (1) NZ184342A (en)
PH (5) PH13557A (en)
PL (4) PL115586B1 (en)
PT (1) PT66694B (en)
RO (4) RO78951A2 (en)
SE (6) SE433079B (en)
SU (2) SU955859A3 (en)
TR (1) TR19652A (en)
YU (4) YU40166B (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1095921A (en) * 1976-08-02 1981-02-17 Thomas M. Brennan Preparation of gamma-pyrones
JPS5444675A (en) * 1977-09-12 1979-04-09 Shin Etsu Chem Co Ltd Production of 3-hydroxy-4-pyrone analog
FR2402654A1 (en) * 1977-09-12 1979-04-06 Shinetsu Chemical Co Tetra:hydro-pyranone derivs. - useful as intermediates for cpds. used as food flavours
JPS5741226U (en) * 1980-08-20 1982-03-05
JPS59135008U (en) * 1983-02-28 1984-09-10 松下電工株式会社 Distribution board device
JPS6050245A (en) * 1983-08-29 1985-03-19 Nissan Motor Co Ltd Fuel injection device in internal-combustion engine
JPH0226945Y2 (en) * 1985-09-11 1990-07-20
JP2586607B2 (en) * 1987-10-30 1997-03-05 日産化学工業株式会社 Production method of optically active alcohol
WO2008116301A1 (en) 2007-03-28 2008-10-02 Apotex Technologies Inc. Fluorinated derivatives of deferiprone
WO2009129592A1 (en) 2008-04-25 2009-10-29 Apotex Technologies Inc. Liquid formulation for deferiprone with palatable taste
ME01911B (en) 2009-07-03 2014-12-20 Apotex Tech Inc Fluorinated derivatives of 3-hydroxypyridin-4-ones
WO2017168309A1 (en) * 2016-03-29 2017-10-05 Dr. Reddy’S Laboratories Limited Process for preparation of eribulin and intermediates thereof
CN108609456B (en) * 2016-12-13 2021-03-12 奥的斯电梯公司 Openable expansion panel and elevator suspended ceiling, elevator car and elevator system with same
CN111606879A (en) * 2020-05-25 2020-09-01 安徽金禾实业股份有限公司 Method for preparing 2-hydroxymethyl-3-alkoxy-4H-pyran-4-ketone by one-pot method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491122A (en) * 1966-09-14 1970-01-20 Monsanto Co Synthesis of 4-pyrones
US3547912A (en) * 1968-07-29 1970-12-15 American Home Prod Derivatives of 2h-pyran-3(6h)-ones and preparation thereof
JPS5145565B1 (en) * 1968-10-12 1976-12-04
US3621063A (en) * 1968-12-24 1971-11-16 Monsanto Co Unsaturated acyclic ketones
US3832357A (en) * 1971-05-26 1974-08-27 Daicel Ltd Process for preparation of 3-hydroxy-2-alkyl-4-pyrone
JPS5212166A (en) * 1975-07-17 1977-01-29 Tatsuya Shono Process for preparation of 4-pyron derivatives
IE42789B1 (en) * 1975-08-28 1980-10-22 Pfizer Preparation of gamma-pyrones
CA1095921A (en) * 1976-08-02 1981-02-17 Thomas M. Brennan Preparation of gamma-pyrones

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FI72723C (en) 1987-07-10
NL8105538A (en) 1982-04-01
JPS5814433B2 (en) 1983-03-18
IE45644B1 (en) 1982-10-20
GB1538374A (en) 1979-01-17
HU185686B (en) 1985-03-28
FI831704L (en) 1983-05-16
ES470745A1 (en) 1979-01-16
PT66694B (en) 1978-11-17
SE8200522L (en) 1982-01-29
PL215007A1 (en) 1979-12-17
CH626357A5 (en) 1981-11-13
HK30381A (en) 1981-07-10
DE2728499C2 (en) 1986-04-03
NO150560B (en) 1984-07-30
NL182805C (en) 1988-05-16
FI72721C (en) 1987-07-10
CA1095921A (en) 1981-02-17
DK153484B (en) 1988-07-18
CH625798A5 (en) 1981-10-15
CH625235A5 (en) 1981-09-15
CA1110254A (en) 1981-10-06
DE2760221C2 (en) 1989-10-05
JPS5618597B2 (en) 1981-04-30
NL8105540A (en) 1982-04-01
IE790587L (en) 1978-02-02
NO150561C (en) 1984-11-07
PH13926A (en) 1980-11-04
JPS5436267A (en) 1979-03-16
SE8200520L (en) 1982-01-29
PH14625A (en) 1981-10-12
SU955859A3 (en) 1982-08-30
HK30681A (en) 1981-07-10
NO150043B (en) 1984-04-30
FI73424B (en) 1987-06-30
PL115496B1 (en) 1981-04-30
DK154079B (en) 1988-10-10
DE2760220C2 (en) 1987-08-20
DK153483B (en) 1988-07-18
JPS5436269A (en) 1979-03-16
IE790586L (en) 1978-02-02
AT363470B (en) 1981-08-10
FI831704A0 (en) 1983-05-16
MY8100267A (en) 1981-12-31
MY8100287A (en) 1981-12-31
SE445042B (en) 1986-05-26
NO821850L (en) 1978-02-03
BR7703970A (en) 1978-07-04
YU42613B (en) 1988-10-31
SE8200521L (en) 1982-01-29
HK30481A (en) 1981-07-10
FI771934A (en) 1978-02-03
IE45641B1 (en) 1982-10-20
ATA124380A (en) 1981-03-15
HU180040B (en) 1983-01-28
IE790584L (en) 1978-02-02
ES470743A1 (en) 1979-01-16
PL115497B1 (en) 1981-04-30
HU185687B (en) 1985-03-28
FI72720B (en) 1987-03-31
CS203921B2 (en) 1981-03-31
DK326186D0 (en) 1986-07-09
FI72722C (en) 1987-07-10
YU270382A (en) 1983-10-31
ATA124480A (en) 1981-01-15
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ES470744A1 (en) 1979-01-16
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PL115586B1 (en) 1981-04-30
RO74367A (en) 1981-11-24
SE8200518L (en) 1982-01-29
YU146977A (en) 1983-06-30
DK276177A (en) 1978-02-03
FI831702L (en) 1983-05-16
DK326186A (en) 1986-07-09
MX4597E (en) 1982-06-25
DK326086D0 (en) 1986-07-09
NO821848L (en) 1978-02-03
TR19652A (en) 1979-09-17
BG28849A3 (en) 1980-07-15
JPS5436266A (en) 1979-03-16
NL182477B (en) 1987-10-16
BG29136A3 (en) 1980-09-15
FR2372821B1 (en) 1980-10-17
SE8200519L (en) 1982-01-29
ES459994A1 (en) 1978-11-16
FI831703L (en) 1983-05-16
JPS5436271A (en) 1979-03-16
YU166383A (en) 1986-02-28
NO150042C (en) 1984-08-15
FI72721B (en) 1987-03-31
EG13080A (en) 1981-03-31
NL182805B (en) 1987-12-16
HU186026B (en) 1985-05-28
SU1015826A3 (en) 1983-04-30
NO150560C (en) 1984-11-07
GB1538373A (en) 1979-01-17
NL170955C (en) 1983-01-17
NL182476B (en) 1987-10-16
CS203923B2 (en) 1981-03-31
BG28988A4 (en) 1980-08-15
HK30781A (en) 1981-07-10
ES470746A1 (en) 1979-01-16
NO834236L (en) 1978-02-03
FI831702A0 (en) 1983-05-16
NO772193L (en) 1978-02-03
NO151365B (en) 1984-12-17
DK153484C (en) 1988-11-28
GB1538371A (en) 1979-01-17
ATA440477A (en) 1980-11-15
IT1106258B (en) 1985-11-11
IE45642B1 (en) 1982-10-20
FI72723B (en) 1987-03-31
RO78951A2 (en) 1982-04-12
JPS5420500B2 (en) 1979-07-23
NL182477C (en) 1988-03-16
JPS5318578A (en) 1978-02-20
CA1117541A (en) 1982-02-02
FI72119B (en) 1986-12-31
FI831701A0 (en) 1983-05-16
LU77600A1 (en) 1978-02-01
PH13874A (en) 1980-10-24
YU40166B (en) 1985-08-31
NL170955B (en) 1982-08-16
FI73424C (en) 1987-10-09
GB1538375A (en) 1979-01-17
CS203922B2 (en) 1981-03-31
CH626358A5 (en) 1981-11-13
SE445041B (en) 1986-05-26
AT362790B (en) 1981-06-10
PT66694A (en) 1977-07-01
DK326086A (en) 1986-07-09
NO151365C (en) 1985-03-27
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NL8105539A (en) 1982-04-01
SE444565B (en) 1986-04-21
YU43190B (en) 1989-04-30
YU274782A (en) 1983-12-31
NO821847L (en) 1978-02-03
DK153401C (en) 1988-11-28
FI72720C (en) 1987-07-10
MY8100262A (en) 1981-12-31
NO150042B (en) 1984-04-30
SE444564B (en) 1986-04-21
AT364356B (en) 1981-10-12
FI72722B (en) 1987-03-31
HK30581A (en) 1981-07-10
FI831700L (en) 1983-05-16
FI72119C (en) 1987-04-13
FR2372821A1 (en) 1978-06-30
RO78953A (en) 1982-04-12
IE790585L (en) 1978-02-02
JPS5729034B2 (en) 1982-06-19
DE2728499A1 (en) 1978-02-09
NL7706811A (en) 1978-02-06
IE45641L (en) 1978-02-02
NL182478B (en) 1987-10-16
PL199798A1 (en) 1979-08-27
NO821851L (en) 1978-02-03
JPS5618596B2 (en) 1981-04-30
NO150559C (en) 1984-11-07
JPS5436268A (en) 1979-03-16
NO150561B (en) 1984-07-30
DK153483C (en) 1988-11-28
NO821849L (en) 1978-02-03
GB1538372A (en) 1979-01-17
BE855965A (en) 1977-12-21
NZ184342A (en) 1978-09-25
PH15185A (en) 1982-09-10
FI831701L (en) 1983-05-16
PL215006A1 (en) 1979-12-17
IE45645B1 (en) 1982-10-20
DK154079C (en) 1989-02-27
DK325986A (en) 1986-07-09
AU2601777A (en) 1978-09-21
NO150043C (en) 1984-08-15
RO78952A (en) 1982-04-12
NL182476C (en) 1988-03-16
GR68938B (en) 1982-03-29
DK325986D0 (en) 1986-07-09
FI831703A0 (en) 1983-05-16
PL215008A1 (en) 1979-12-17
DD132494A5 (en) 1978-10-04
FI831700A0 (en) 1983-05-16
AR216080A1 (en) 1979-11-30

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