SE433078B - PROCEDURE FOR PREPARING BETA PYRONS AND INTERMEDIATE PRODUCTS FOR USE IN PREPARATION OF ETHYL MALTOL - Google Patents
PROCEDURE FOR PREPARING BETA PYRONS AND INTERMEDIATE PRODUCTS FOR USE IN PREPARATION OF ETHYL MALTOLInfo
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- SE433078B SE433078B SE7910630A SE7910630A SE433078B SE 433078 B SE433078 B SE 433078B SE 7910630 A SE7910630 A SE 7910630A SE 7910630 A SE7910630 A SE 7910630A SE 433078 B SE433078 B SE 433078B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Saccharide Compounds (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Compounds Of Unknown Constitution (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyridine Compounds (AREA)
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Description
7906416-ß 2 Cl 0 l /\N c cH/ \c-NH C\ lg D H. Å 2 ñññl \\C// I _\ ï/ šo + Hmíè N\ /c\\ +nc1 + H20 ~ N o I (I) O N\ (il / o -\ c / N n/ šïk-Cl /:\ / N C CH \C' \N/ \o+so +N »Ü I - - I 2 2 N C .\1'~1/ \\o o g+soc12' > (I) vilka ej är kända genom litteraturen. 7906416-ß 2 Cl 0 l / \ N c cH / \ c-NH C \ lg D H. Å 2 ñññl \\ C // I _ \ ï / šo + Hmíè N \ / c \\ + nc1 + H20 ~ N o I (I) ON \ (il / o - \ c / N n / šïk-Cl /: \ / NC CH \ C '\ N / \ o + so + N »Ü I - - I 2 2 NC. \ 1 '~ 1 / \\ oo g + soc12'> (I) which are not known in the literature.
Väsentligen innebär detta att 5-kloro-4-amino-24 -fenyl-3(2H)-pyridazinon först bringas reagera med natriumnitrit i koncentrerad HC1 vid låg temperatur . under sådana betingelser att endast ISO-PCA löses fullstän~ digt, varefter man späder med vatten och filtrerar för framställning av en fast kemisk produkt, som ej är känd inom detta område eller från litteraturen, vilken pro-i dukt oväntat härrör från diazotering av aminogruppen i utgângsföreningen och från efterföljande eliminering av HC1 under ringslutning.Essentially, this means that 5-chloro-4-amino-24-phenyl-3 (2H) -pyridazinone is first reacted with sodium nitrite in concentrated HCl at low temperature. under such conditions that only ISO-PCA is completely dissolved, then diluted with water and filtered to produce a solid chemical product not known in the art or from the literature, which product unexpectedly results from diazotization of the amino group in the starting compound and from subsequent elimination of HCl during cyclization.
I ett andra steg bringas den okända kemiska före- gning, som erhålles i det första steget, vilken före- nings struktur bekräftas genom olika typer av analyser -3- 791063Û~8 / \ Rugx X2/R OH O '_______è 03 eller elextroläš CHO {" H J: _ R OR' R' HOH Ä R E+ OH \/ x + g /Hço Bas /Hzo ' R' _ H20; . R'O p» |w Mellanprodukter: R'=C1_5 alkyl R=väte, allyl, aryl. èlkenyl. èralkyl Slptprßdflkt (51: R=vëte, alkyl, alkenyl, aryl, aralkyl R=H, pyromekonsyra R=CH3, maltol R=CH2CH3, etylmaltol.In a second step is brought the unknown chemical compound obtained in the first step, which structure of the compound is confirmed by various types of analyzes -3- 791063Û ~ 8 / \ Rugx X2 / R OH O '_______ è 03 or elextroläš CHO {"HJ: _ R OR 'R' HOH Ä R E + OH \ / x + g / Hço Bas / Hzo 'R' _ H20;. R'O p» | w Intermediates: R '= C1-5 alkyl R = hydrogen, allyl, aryl, alkenyl, eralkyl Slptprßd fl kt (51: R = hydrogen, alkyl, alkenyl, aryl, aralkyl R = H, pyromeconic acid R = CH3, maltol R = CH2CH3, ethylmaltol.
Furfuralreaktionen med ifrågavarande Grignard-reagens beskrivs i Chemical Abstracts 44, (1950) sid. lO92d.The furfural reaction with the Grignard reagent is described in Chemical Abstracts 44, (1950) p. lO92d.
Framställningen av mellanprodukten 2 (R = H) genom elektrolys i metanol beskrivs i det amerikanska patentet 2.714.576 och Acte. Chem.The preparation of intermediate 2 (R = H) by electrolysis in methanol is described in U.S. Patent 2,714,576 and Acte. Chem.
Scand. 6, (1952) sid. 545. Syntesen. vari brom í metanol användes angee í Ann. 526 (1935) sid. 231. Üen allmänna iden att använda klor i ett alkoholhaltigt lösningsmedel är även välkänd (jämför ewompelvís den brittiska patentskrifte š§5,Ü41). Man har under ¥örFarandet enli H 2 liggande upp¥ínning äunniz att reaktionen mellan mellanprodukten 1 och klcr í ett alkoholhaltígt lösningsmedel vid en temperatur mellan -70 ocn 5008 ger en ren överëäring till den önskade mellanprodukten Z med HCB-bíprodukten neutralíserad genom en bas såsom ammoniak. natríum- karaonat eller andra alkalímetallbaser. Fastän den tidigare líttereturï ïfï5;@ïï5“ï5 denna rea? inn ger utbyten upp till ungefär 501 ger För- lf' t För 7910630-8 -4 - farandet enligt Föreliggande uppFínning utbyten över 33%.Scand. 6, (1952) p. 545. The synthesis. wherein bromine in methanol was used angee in Ann. 526 (1935) p. 231. The general idea of using chlorine in an alcoholic solvent is also well known (cf. ewompelvís British Patent Specification š§5, Ü41). It has been found in the process according to the H2 invention that the reaction between intermediate 1 and chlorine in an alcoholic solvent at a temperature between -70 ° C and 5008 gives a pure conversion to the desired intermediate Z with the HCB by-product neutralized by a base such as ammonia. sodium karaonate or other alkali metal bases. Although the previous líttereturï ïfï5; @ ïï5 “ï5 this sale? inn gives yields up to about 501 gives För- lf 't For 7910630-8 -4 - the procedure according to the present invention yields over 33%.
Nellanprodukten Å (R = CH3] beskrivs i Acta. Chem. Scand 9, [1955] sid. 17 och Tetrahedron 27, (1971) sid. 157 e 2 (R = CHZCHSJ är ah ny förening som kan framställas genom tidigare be- (U . llanproduktsz skrivna sätt. _ Behandlingen av mellanprodukten 2 med en stark organisk syra är ny och ger det önskade B-alkoxiderivatet Q direkt i högt utbyte och undviker bildning av motsvarande hydroxíderivat vilka är mycket insta- bila vid ytterligare reaktioner. Mellanprodukten 2 bringas i kontakt med en syra, som huvudsakligen är vattentri, tastän närvaron av ett protiskt lösningsmedel såsom en alkohol eller en liten mängd vatten är Fördelaktigt. E¥ter behandlingen separeras produkten i ett tillstånd av renhet, som är lämpligt för överföring till mellanprodukten Q, från syramediet genom konventionell extraktionsteknik. Fastän myrsyra och tritluorättiksyra Föredrages kan vilka som helst syror med ett pKa av ungetär 4 eller därunder överföra mellanprodukten 2 till den önskade *mellanprodukten Ä. Andra lämpliga organiska syror innefiattar p-toluen- sultonsyra, metansulronsyra, citronsyra, oxalsyra och klorättiksyra; lämpliga mineralsyror innefattar svavelsyra, saltsyra och Fostorsyra.The nellan product Å (R = CH3] is described in Acta. Chem. Scand 9, [1955] p. 17 and Tetrahedron 27, (1971) p. 157 e 2 (R = CHZCHSJ is ah new compound which can be prepared by previous The treatment of intermediate 2 with a strong organic acid is new and gives the desired β-alkoxide derivative Q directly in high yield and avoids the formation of corresponding hydroxide derivatives which are very unstable in further reactions. contact with an acid which is essentially aqueous, the presence of a protic solvent such as an alcohol or a small amount of water is advantageous.After the treatment, the product is separated in a state of purity suitable for transfer to intermediate Q from the acid medium Although conventional formic acid and tritluoroacetic acid are preferred, any acids having a pKa of less than 4 or less can transfer intermediate 2 to the desired * intermediate Ä. other suitable organic acids include p-toluenesultonic acid, methanesulronic acid, citric acid, oxalic acid and chloroacetic acid; Suitable mineral acids include sulfuric acid, hydrochloric acid and Fosteric acid.
Sura hartser såsom Amberlit GC-120 och Dowex SÜW kan även användas.Acidic resins such as Amberlit GC-120 and Dowex SÜW can also be used.
Epoxidationen av mellanprodukten Q till epoxikazonan Q år även ett nytt Förfarawde. Nellanprodukten Q upplöses i ett lämpligt lösning: medel såsom vatten eller alkohol såsom isopropylalkohcl eller metanol.The epoxidation of the intermediate Q to the epoxy zone Q is also a new process. The nellan product Q is dissolved in a suitable solution: agents such as water or alcohol such as isopropyl alcohol or methanol.
En bas såsom natriumbirkarbonat eller natriumhydroxid tillsättes ešíer tillsatsen av H202 (30%). Den önskade mellanprodukten 2 kan separaras genom konventionell extraktionsteknik och år lämplig För utvinning av den önskade pyronen § utan ytterligare rening. _ Den slutliga omfördelningen av epoxiketonerna i till gamma- pyronerna ä är dy och sker i gott utbyte och med stor renhet. Mellan- produkten Q bringas till reaktion i ett surt medium och den eFter¥öljsn- de isoleringen av den önskade gammapyronen ä sker genom konventionell kristallísations~ eller extraktionsteknik. Den rena garespyronen kan omkristalliseras ur ett lämpligt lösningsmedel såsom isepropanol, metanol eller vatteñ. Fastän het vattenhaltig míneralsyra såsom svavel- syra eller saltsyra är den mest lämpliga metoden tör att överföra mallar produkten Q till produkten Å kan den önskade gammapyronen tramställas med Lewis-syror såsom bortrifluorideterat, zinkklorid :ah tenntetra- klorid; genom sura jonhartser såsom Amberlit GC-120 eller Dowex SOM och med starka organiska syror såsom p-toluensulfonsyra eller myrsyra. -s- 7910630-8 Föreningar. som utgör mollanprodukten R = CH20~alkyl) kan framställas ur kolvätekällo Accounts oF Chemical Research B, (1975) sid. 192. šnligt Förfarandut Q (F = CHZÜH eller r såsom beskrivits i enligt töreligganoe uppfinning kan dessa Föreningar överföras till mellanprodukterna 3 och produkten ä vari R = EH2DH eller CH20-alnyl.A base such as sodium bircarbonate or sodium hydroxide is added or the addition of H 2 O 2 (30%). The desired intermediate 2 can be separated by conventional extraction technique and is suitable for recovering the desired pyrone § without further purification. The final redistribution of the epoxy tones in to the gamma-pyrones ä is dy and takes place in good yield and with great purity. The intermediate Q is reacted in an acidic medium and the subsequent isolation of the desired gamma pyrone is effected by conventional crystallization or extraction techniques. The pure gare pyrone can be recrystallized from a suitable solvent such as isepropanol, methanol or water. Although hot aqueous mineral acid such as sulfuric acid or hydrochloric acid is the most suitable method for transferring templates product Q to product Å, the desired gamma pyrone can be triturated with Lewis acids such as boron trifluoride etherate, zinc chloride: ah tin tetrachloride; by acidic ionic resins such as Amberlit GC-120 or Dowex SOM and with strong organic acids such as p-toluenesulfonic acid or formic acid. -s- 7910630-8 Associations. which constitutes the molar product R = CH 2 O-alkyl) can be prepared from hydrocarbon source Accounts oF Chemical Research B, (1975) p. 192. According to Process Q (F = CH 2 OH or r as described in the present invention, these Compounds may be converted to intermediates 3 and the product wherein R = EH 2 DH or CH 2 O-alnyl.
Produkten ä (R = Cfi20H eller CH2D-alkyll kan överFöras till maltol såsom beskrivits i det amerikanska patentet 3,130,234 eller Angew.The product ä (R = C20 H or CH2D-alkyl can be converted to maltol as described in U.S. Patent 3,130,234 or Angew.
Chem. 81, (1959) sid. 995.Chem. 81, (1959) p. 995.
Uppfinningen âskådliggöres närmare medelst Följande exempel vari temperaturen avser Celsius-grader.The invention is further illustrated by the following examples in which the temperature refers to degrees Celsius.
Exeoel 1.Exeoel 1.
I en 3-halsad kolv med rund botten utrustad med en magnetisk omrörare, en mantlad tillsatstratt, en termometer och en torr iskon- densor sattes 22,4 g (0,2 mol) av mellanprodukten 1 (R = CH3), 100 nl metanol och 21,1 g (0,2 mol) natriumkarbonat och denna blandning kyldes till OD med användning av ett is-aoetonbad. Till denna snabbt omrörda -lösning sattes däreFter droppvis en kall (-300) lösning av klor, (11,Û ml. 0,24 mol) i metanol. Tillsatsen av klor ksntrollerades För att hålla reaktionstemperaturen under 400. Tillsatsen erfordrade un sFë: 2 timmar. Etter tillsatsen omrördes reaktionsblandníngen vid isbad- temperatur i 30 minuter och ïiok däre?ter uppvärmas till rumstemperatur.In a 3-neck round bottom flask equipped with a magnetic stirrer, a jacketed funnel, a thermometer and a dry ice condenser was added 22.4 g (0.2 mol) of the intermediate 1 (R = CH 3), 100 nl of methanol and 21.1 g (0.2 mol) of sodium carbonate and this mixture was cooled to OD using an ice-acetone bath. To this rapidly stirred solution was then added dropwise a cold (-300) solution of chlorine, (11.1 ml, 0.24 mol) in methanol. The addition of chlorine was controlled to keep the reaction temperature below 400. The addition required un sFë: 2 hours. After the addition, the reaction mixture was stirred at ice bath temperature for 30 minutes and then warmed to room temperature.
Den erhållna uppslsmningen Filtrerades; metanolen evlägsnadss i vakuum. återstoden togs upp i bensen och passerades genom en aluminíumkropp som slutligt ¥ilter. Eensenen avlägsnades och gav 31,9 g (91%) av den J. önskade dimetoxidihydroturanen 2 (R = CH3, R' = CH Detta material 3 kan användas utan ytterligare rening eller kan destilleras, kokpunkt 7s-7s°/s mm [104-107910-11 mm. Acta Chem. scana. 9. (1955) sia oj.The resulting solution was filtered; the methanol is removed in vacuo. the residue was taken up in benzene and passed through an aluminum body which was finally filtered. The enensen was removed to give 31.9 g (91%) of the J. desired dimethoxy dihydroturane 2 (R = CH 3, R '= CH This material 3 can be used without further purification or can be distilled, boiling point 7s-7s ° / s mm [104 -107910-11 mm Acta Chem. Scana 9. (1955) sia oj.
Analys: Beräknat För CBH14Ü4: C, 55,22 H, 8,11 Funnet: C, 55,34 H, 8,04 Exempel 2.Analysis: Calculated for CBH 14 U 4: C, 55.22 H, 8.11 Found: C, 55.34 H, 8.04 Example 2.
Sättet enligt exempel 1 upprepades med mellanprodukten 1 (R = H) och gav mellanprodukten 2 (R = H, R' = CH3), kokpunkt so-sf/s mm f71°/1,a mm Tetrshearan 27, (1971) sia. 1973].The procedure of Example 1 was repeated with the intermediate 1 (R = H) to give the intermediate 2 (R = H, R '= CH 3), boiling point so-sf / s mm f71 ° / 1, a mm Tetrshearan 27, (1971) sia. 1973].
Exempel 3.Example 3.
Sättet enligt exempel 1 upprepades med mellanprodukten 1 (R = H] och gav mellanprodukten 2 (R = H, R' = CH3], kokpunkt 1020/10 mr 7910630-8 - s - Analys: Beräknat för C9H1604: C, 57,50 H, 8,50_ Funnet: C. 57,39 H, 8,59 Exempel 4.The procedure of Example 1 was repeated with the intermediate 1 (R = H] to give the intermediate 2 (R = H, R '= CH 3], b.p. 1020/10 mr 7910630-8 - s - Analysis: Calculated for C 9 H 16 O 4: C, 57.50 H, 8.50 Found: C, 57.39 H, 8.59 Example 4.
Sättet enligt exempel 1 upprepades med användning av mellan- produkten 1 (R = ßH3] och metanolen ersattes med iscpropanol till mellanprodukten à [R = CH3, R' = CH(CH3)2], kokpunkt 62-540/0,05 mm.The procedure of Example 1 was repeated using intermediate 1 (R = ßH3] and the methanol was replaced with ispropanol to the intermediate à [R = CH3, R '= CH (CH3) 2], b.p. 62-540 / 0.05 mm.
Exempel 5. ' Sättet enligt exempel 1 upprepades med användning av brom i stället För klor och med användning av mellanprocukten 1 och gav mellanprodukten Ä vari R betecknar väte, metyl, etyl, hexyl. Fenyl, vinyl, 1-butenyl, allyl och 1-hexenyl och R' betecknar metyl, etyl, isopropyl och hexyl.Example 5. The procedure of Example 1 was repeated using bromine instead of chlorine and using intermediate 1 to give intermediate Ä wherein R represents hydrogen, methyl, ethyl, hexyl. Phenyl, vinyl, 1-butenyl, allyl and 1-hexenyl and R 'represent methyl, ethyl, isopropyl and hexyl.
Exempel 5.Example 5.
I ett litet glaselektrolyskärl med en kolanod och nickelkatod placerades 50 ml metanol, 0,5 ml koncentrerad svavelsyra och 1,12 g '(0,01 mol] av mellanprodukten 1 (R = CH3, R' = BH3) och lösningen kyl- des till -200. Elektrolys skedde däre¥ter med använining av ett poten- tiostat/galvanostat Princeton Applied Research Corporation Model 373 - instrument som inställdes för att avge en konstant strömstyrka av 0,6 ampere. Efter en reaktionstid av 30 minuter hälldes reaktionspro~ dukten i vatten och prudukten E [R = CH3. R' = CH3) isolerades genom kloroFormextraktion. Detta förfarande liknar det som beskrivs i det amerikanska patentet 2,714,576 men svavelsyra ersattes av ammonium- bromid som elektrolyt.In a small glass electrolytic vessel with a carbon anode and nickel cathode were placed 50 ml of methanol, 0.5 ml of concentrated sulfuric acid and 1.12 g '(0.01 mol] of the intermediate 1 (R = CH 3, R' = BH 3) and the solution was cooled Electrolysis was then performed using a potentiostat / galvanostat Princeton Applied Research Corporation Model 373 instrument which was set to deliver a constant current of 0.6 amperes.After a reaction time of 30 minutes the reaction product was poured in water and the product E [R = CH 3. R '= CH 3) was isolated by chloroform extraction. This process is similar to that described in U.S. Patent 2,714,576, but sulfuric acid was replaced by ammonium bromide as electrolyte.
Exempel 7.Example 7.
Sättet enligt exempel É upprepades med mellenprodukten l och gav mellanprodukten 3 vari R betecknar väte, etyl, hexyl, Fenyl, bensyl. 7 vinyl, allyl, 1-butenyl och 1-hexenyl och R' betecknar etyl, ísopropyl och hexyl.The procedure of Example E was repeated with intermediate 1 to give intermediate 3 wherein R represents hydrogen, ethyl, hexyl, phenyl, benzyl. 7 vinyl, allyl, 1-butenyl and 1-hexenyl and R 'represents ethyl, isopropyl and hexyl.
Exempel B.Example B.
Till en 2-liters kolv med tre halsar och rund botten, utrustad med en magnetisk omrörare, dropptratt och en termometer sattes 400 ml myrsyra och 20 ml metanol. Till denna lösning sattes en lösning av mellanprodukten Å (R = CH3, R' = CH3), 104,4 g, 0,6 mol i 40 ml metanol.To a 2-liter flask with three necks and round bottom, equipped with a magnetic stirrer, dropping funnel and a thermometer were added 400 ml of formic acid and 20 ml of methanol. To this solution was added a solution of the intermediate Å (R = CH 3, R '= CH 3), 104.4 g, 0.6 mol in 40 ml of methanol.
Den droppvisa tillsatsen skedde under 15 minuter. Reaktionsblandningen hälldes i 1 l vatten och extraherades tre gånger med 500 ml-portioner kloroform. 0e kombinerade kloro¥ormtvâttvätskorna tvättades med natrium- bikarbonatvattenlösning och saltlake. Kloro¥ormlösningen indunstades till ett orent utbyte av 78 g (69%) av mellanprodukzen Q (R = CH3, R' = CH3) som ljust brun produkt. Üetorena materialet kan användas som 7910630-8 såcant eller destilleras vid 2 mm tryck, 50-520 L82-B50/30 mm, Tetra- hecfan 27, (1971) sia 1973].The dropwise addition took place over 15 minutes. The reaction mixture was poured into 1 l of water and extracted three times with 500 ml portions of chloroform. The combined chlorine washes were washed with sodium bicarbonate aqueous solution and brine. The chlorine solution was evaporated to a crude yield of 78 g (69%) of the intermediate Q (R = CH3, R '= CH3) as a light brown product. The Üetorena material can be used as 7910630-8 as such or distilled at 2 mm pressure, 50-520 L82-B50 / 30 mm, Tetrahecfan 27, (1971) sia 1973].
Exempel 9.Example 9.
Sättet enligt exempel 6 upprepades med analoga mellanprodukta: 3 (R = H, R' = CH3l till mellanprodukten Ä (R = H, R' so-eß°/14 mm [75-a1°/23 mm, Tetrahearan 27, (1971) sia. 1973].The procedure of Example 6 was repeated with analogous intermediates: 3 (R = H, R '= CH31 to the intermediate Ä (R = H, R' so-eß ° / 14 mm [75-a1 ° / 23 mm, Tetrahearan 27, (1971)). ) sia 1973].
Exempel 10.Example 10.
= CH3), kokpunkt Sättet enligt exempel B upprepadee med mellanprodukten E (R = CH7CH3, R' = CH3) till mellanprodukten Q [R = CH CH R' = CH3). kukpunkt 79-eo°/14 mm.= CH3), boiling point The procedure of Example B repeated with the intermediate E (R = CH7CH3, R '= CH3) to the intermediate Q [R = CH CH R' = CH3). boiling point 79 ° C / 14 mm.
Exempel 11. 2 3' Sättet enligt exempel B upprepades med mellanprodukten 3 och gav mellanprodukten Q vari R betecknar hexyl, Fenyl, bensyl, vinyl, allyl, 1-butenyl och 1-hexenyl och R betecknar isopropyl ooh hexyl.Example 11. 2 3 'The procedure of Example B was repeated with intermediate 3 to give intermediate Q wherein R represents hexyl, phenyl, benzyl, vinyl, allyl, 1-butenyl and 1-hexenyl and R represents isopropyl and hexyl.
Exempel 12. ' Sättet enligt exempel 8 upprepades med jämFörbara resultat -under ersättning av myrsyran med en organisk syra såsom citronsyra. oxelsyra, klorättiksyra. p-toluensulfonsyra, metansulëonsyra och tri- fluorättiksyra. I laboratoriet gav trifluorättiksyra ett 83%-igt ut- byte av 3 (R=R'=CH3) med användning av sättet enligt exempel 8. Med framgång användes vid denna överföring även klorättiksyra, p~to1uen- sulfonsyra, metansulfonsyra och oxalsyra, fastän i lägre utbyten.Example 12. The procedure of Example 8 was repeated with comparable results - replacing the formic acid with an organic acid such as citric acid. oxelic acid, chloroacetic acid. p-toluenesulfonic acid, methanesuleneic acid and trifluoroacetic acid. In the laboratory, trifluoroacetic acid gave an 83% yield of 3 (R = R '= CH3) using the method of Example 8. Successfully used in this transfer were also chloroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and oxalic acid, although in lower yields.
Exempel 13. _ I en 3-halsad kolv med rund botten utrustad med en tillsats- tratt, lågtemperaturtermometer och omrörare Framställdes en lösning av ,0 g (0.029 mol) av mellanprodukten 2 (R = CH3, R' = CH3l i dietyleter (10 ml] och lösningen kyldes till -400. Till denna lösning sattes crorp vis 1,5 ml koncentrerad svavelsyra och den svart; blandningen omrördes i 5 minuter vid -400, hälldes i vatten och den önskade mellanprodukten Q (R = CH3, R' = CH3l isolerades enligt sättet som beskrivits i exum« pel B.Example 13. In a 3-necked round bottom flask equipped with an addition funnel, low temperature thermometer and stirrer A solution of .0 g (0.029 mol) of the intermediate 2 (R = CH3, R '= CH31 in diethyl ether (10 To this solution was added cramped 1.5 ml of concentrated sulfuric acid and the black, the mixture was stirred for 5 minutes at -400, poured into water and the desired intermediate Q (R = CH 3, R '= CH 31 was isolated according to the procedure described in Example B.
Huvudsakligen samma resultat erhölls när svavelsyran ersattes med saltsyra eller Fos¥orsyra.Substantially the same results were obtained when the sulfuric acid was replaced by hydrochloric acid or phosphoric acid.
Exempel 10.Example 10.
Till en torr kolv sattes 1,05 g (0.0074 mel) av me1lanprunuLï,r Q (R = CH3, R' = CH30J löst i 20 ml isoprooylalkohol och kolven kyldes till 00. 0äreFter tillsattes 0,5 g [0,0059 moll natriumbikarbonat och 2,0 ml 10.023 mol) 30%-ig väteperoxid och reaktionen omrërdes vid rums- temperatur i 2 timmar. Reaktionsblandningen hälldes i 100 ml vatten och vattnet extraherades med kloroForm, följd av kancentration till en olja. som destillerades vid 70-000/3 mm. Ett analytiskt prov renades genom gaskromatografi. 7910650-s -8- Analys: Beräknat För C7H1ÛÜ4= C. 53,16 H. 5.37 Funnet: C, 52,90 H, 5,27 Exempel 15.To a dry flask was added 1.05 g (0.0074 mol) of methylprunul, Q (R = CH 3, R '= CH 3 O) dissolved in 20 ml of isoproyl alcohol and the flask was cooled to 00. Then 0.5 g [0.0059 mol of sodium bicarbonate was added and 2.0 ml of 10,023 mol) of 30% hydrogen peroxide and the reaction was stirred at room temperature for 2 hours. The reaction mixture was poured into 100 ml of water and the water was extracted with chloroform, followed by concentration to an oil. which was distilled at 70-000 / 3 mm. An analytical sample was purified by gas chromatography. 7910650-s -8- Analysis: Calculated for C 7 H 16 O 4 = C. 53.16 H. 5.37 Found: C, 52.90 H, 5.27 Example 15.
Sättet enligt exempel 14 upprepades med mellanprodukten Q [R = H, R' = CH3) till mellanprodukten 4 (R = H, R' = CH3].The procedure of Example 14 was repeated with the intermediate Q [R = H, R '= CH 3) to the intermediate 4 (R = H, R' = CH 3].
Analys: C, 50,00 H, 5,59 C, 50,09 H, 5,81 Beräknat För CEHBÜÅ: Funnet: Exempel 16.Analysis: C, 50.00 H, 5.59 C, 50.09 H, 5.81 Calculated for CEHBÜÅ: Found: Example 16.
Sättet enligt exempel 14 upprepades med mellanprodukten Q (R = CHZCHB, R' = CH3] till mellanprodukten 4 (R = CHZCHS, R' = CH3).The procedure of Example 14 was repeated with the intermediate Q (R = CH 2 CHB, R '= CH 3] to the intermediate 4 (R = CH 2 CHS, R' = CH 3).
Analys: Beräknat För C H 0 C, 55,51- H, 7,02 a 12 4' __ Funnet: C, 55,95 JH, 7,04 Exempel 17.Analysis: Calculated for C H 0 C, 55.51-H, 7.02 and 12 4 '__ Found: C, 55.95 JH, 7.04 Example 17.
Sättet enligt exempel 14 upprepades med mellanprodukten Q till mellanprodukten 4 vari R betepknar hexyl, Fenyl, bensyl, vinyl, allyl, 1-butenyl och 1-hexenyl och R' betecknar isopropyl och hexyl.The procedure of Example 14 was repeated with the intermediate Q to the intermediate 4 wherein R represents hexyl, Phenyl, benzyl, vinyl, allyl, 1-butenyl and 1-hexenyl and R 'represents isopropyl and hexyl.
Exempel 18.Example 18.
Till en 75 ml kolv sattes 2,84 g (0,02 moll av mellanprodukten Q [R = CH3, R' = CH3), 10 ml vatten och 10 ml isopropanol. Lösningen kyldes till 0-5D och pH justerades till 7,0-9,0 med 1 N Na0H. 0äreFter tillsattes 2,1 ml 30%-ig väteperoxid droppvis tillsammans med Na0H som även tillsattes tör att bibehålla konstant pH. Kylning er¥ordrades För att hålla satstemperaturen under 100. Efter tillsats av peroxid omrör- des reaktionsblandningen vid 8-100 i unge¥är 1 timme, hälldes i vatten och lösningen extraherades med kloro¥orm. Lösningsmedlet avlägsnades I 3, R' = CH3] Sum klar olja. Reaktionstemperatur över 150 och pH över 9,5 eller under 5,5 ..»-.,\ och gav 2,99 g (94,:ø; av mellanprodukten 4 (R = CH gav lägre utbyte av mellanprodukten 4.To a 75 ml flask was added 2.84 g (0.02 mol of the intermediate Q [R = CH 3, R '= CH 3), 10 ml of water and 10 ml of isopropanol. The solution was cooled to 0-5D and the pH was adjusted to 7.0-9.0 with 1 N NaOH. Then 2.1 ml of 30% hydrogen peroxide was added dropwise together with NaOH which was also added to maintain a constant pH. Cooling was ordered to keep the batch temperature below 100. After the addition of peroxide, the reaction mixture was stirred at 8-100 for about 1 hour, poured into water and the solution was extracted with chlorine. The solvent was removed in 3, R '= CH 3] Total clear oil. Reaction temperature above 150 and pH above 9.5 or below 5.5 .. gave a yield of 2.99 g (94 ° C) of the intermediate 4 (R = CH gave a lower yield of the intermediate 4).
Huvudsakligen samma resultat erhålles när isopropanolen er- sättes med vatten.Essentially the same results are obtained when the isopropanol is replaced with water.
Exempel 19.Example 19.
Till en kolv försedd med kondensor sattes 3,7 Q (0,023 mol) av mellanprodukten 4 [R = CH3, R' = CH3) och 50 ml ZM HZSÜ4. Efter upp- hettning av de två faslösningarna i 1,5 timmar vid âterflöde kyldes reaktionsblandningen. pH justerades till 2.2 med 8 N Na0H, extraherades 3 gånger med vardera 100 ml kloroform ocb de kombinerade lösningsmedels extrakten koncentrerades och gav en produkt 5 (R = CH3, maltol). -9- ' 791Û63Û~8 Sättet enligt exempel 19 upprepades med mellanprcdukten 3 verí R ceteckner väte, etyl, hexyl, tenyl, bensyl,_al1yl, vinyl, 1-buten;1 och 1-hexenyl och R' betecknar metyl, etyl, isoeropyl och hexyl czn gav en prccukt ä vari vari R betecknar väte, etyl, he>yl, Fenyl, tansyl, allyl, vinyl, 1~butenyl och 1-hexenyl.To a flask equipped with a condenser was added 3.7 ((0.023 mol) of the intermediate 4 [R = CH 3, R '= CH 3] and 50 ml of ZM H 2 SO 4. After heating the two phase solutions for 1.5 hours at reflux, the reaction mixture was cooled. The pH was adjusted to 2.2 with 8 N NaOH, extracted 3 times with 100 ml each of chloroform, and the combined solvent extracts were concentrated to give a product (R = CH 3, maltol). The procedure of Example 19 was repeated with the intermediate 3 wherein R represents hydrogen, ethyl, hexyl, tenyl, benzyl, alkyl, vinyl, 1-butene; 1 and 1-hexenyl and R 'represents methyl, ethyl, isoeropyl and hexyl czn gave a product wherein R represents hydrogen, ethyl, heyl, phenyl, tansyl, allyl, vinyl, 1-butenyl and 1-hexenyl.
Sättet enligt exempel 19 upprepaåes med mellanprodukten 4 (R=CH2CH3, ef=cu3) :in etyimaltoi (s,R=cH2cH3), smäupufnft 90-939 sättet upp- repedes med mellenproâukten 4 (H=H, R'=CH3) och gav pyromekonsyre, smeitpwxt 113-115° (5,:=.=H).The procedure of Example 19 is repeated with the intermediate 4 (R = CH 2 CH 3, ef = cu 3): in ethyl malto (s, R = cH 2 cH 3), m.p. 90-939 the procedure was repeated with the intermediate 4 (H = H, R '= CH 3) and gave pyromeconic acid, melting point 113-115 ° (5,: =. = H).
Exempel 21.Example 21.
Till en 250 cma wheaton~pressF1aske sattes 3,16 g (0,Ü2 mal) 3, R' = cH3J och so cma zm HZSU4. Kävlet Förseglades och upphettades till 14Ü~16Ü0 i 1-2 timmar. Eïier kylning av mellanprodukten Q [R = CH skedde reaktionen som beskrivits í exempel 19 och gav maltol (R = CH3).To a 250 cma wheaton ~ pressF1 ash was added 3.16 g (0, Ü2 mal) 3, R '= cH3J and so cma zm HZSU4. The core was sealed and heated to 14Ü ~ 16Ü0 for 1-2 hours. After cooling the intermediate Q [R = CH], the reaction described in Example 19 took place to give maltol (R = CH3).
Exempel 22.Example 22.
Sättet enligt exempel 19 och 20 upprepades med jämförbara resultat varvid svaveleyran ersattes med saltsyra, Dowex SSW och Amberlíåe GC-120.The procedure of Examples 19 and 20 was repeated with comparable results replacing the sulfuric acid with hydrochloric acid, Dowex SSW and Amberlíåe GC-120.
Exempel 23.Example 23.
Till en liten kolv sattes 1,55 g [0,01 mol] av mellanproduk- ten Q (R = CH3. R' = CH3) och 25 ml bensen töljd av 3,7 ml bortri- Fluorideterat. Eêter omrörning i 24 timmar vid 250 avlägsnades läs- ningsmešlet, återstoden extraherades med kloroform och klcroFornen av- lägsnades och gav maltal (R = CH3J.To a small flask was added 1.55 g [0.01 mol] of the intermediate Q (R = CH 3. R '= CH 3) and 25 ml of benzene followed by 3.7 ml of boron trifluoride etherate. After stirring for 24 hours at 250, the bead was removed, the residue was extracted with chloroform and the chloroform was removed to give malt (R = CH 3.
Huvudsakligen samma resultat erhölls när bortritluoridetera- tet ersattes med p-toluensulfonsyra, myrsyra, zinkklcrid eller tenn~ tetraklcrid.Substantially the same results were obtained when the boron trifluoride etherate was replaced with p-toluenesulfonic acid, formic acid, zinc chloride or tin tetrachloride.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60845275A | 1975-08-28 | 1975-08-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| SE7910630L SE7910630L (en) | 1979-12-21 |
| SE433078B true SE433078B (en) | 1984-05-07 |
Family
ID=24436571
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7607321A SE426592B (en) | 1975-08-28 | 1976-06-24 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| SE7910631A SE432929B (en) | 1975-08-28 | 1979-12-21 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS AND INTERMEDIATE PRODUCTS FOR USE IN PREPARATION OF ETHYL MALTOL |
| SE7910630A SE433078B (en) | 1975-08-28 | 1979-12-21 | PROCEDURE FOR PREPARING BETA PYRONS AND INTERMEDIATE PRODUCTS FOR USE IN PREPARATION OF ETHYL MALTOL |
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| Application Number | Title | Priority Date | Filing Date |
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| SE7607321A SE426592B (en) | 1975-08-28 | 1976-06-24 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| SE7910631A SE432929B (en) | 1975-08-28 | 1979-12-21 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS AND INTERMEDIATE PRODUCTS FOR USE IN PREPARATION OF ETHYL MALTOL |
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| JPS52153967A (en) * | 1976-06-15 | 1977-12-21 | Otsuka Chem Co Ltd | 5,6-dihydro-2h-pyran-5-one derivatives |
| CA1095921A (en) * | 1976-08-02 | 1981-02-17 | Thomas M. Brennan | Preparation of gamma-pyrones |
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| US3159652A (en) * | 1962-06-13 | 1964-12-01 | Pfizer & Co C | Preparation of gamma-pyrones |
| US3476778A (en) * | 1966-05-16 | 1969-11-04 | Monsanto Co | Gamma-pyrone synthesis |
| US3491122A (en) * | 1966-09-14 | 1970-01-20 | Monsanto Co | Synthesis of 4-pyrones |
| JPS5145565B1 (en) * | 1968-10-12 | 1976-12-04 | ||
| JPS5212166A (en) * | 1975-07-17 | 1977-01-29 | Tatsuya Shono | Process for preparation of 4-pyron derivatives |
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