GB1593822A - Manufacture of pyridones - Google Patents
Manufacture of pyridones Download PDFInfo
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- GB1593822A GB1593822A GB520578A GB520578A GB1593822A GB 1593822 A GB1593822 A GB 1593822A GB 520578 A GB520578 A GB 520578A GB 520578 A GB520578 A GB 520578A GB 1593822 A GB1593822 A GB 1593822A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
(54) MANUFACTURE OF PYRIDONES
(71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock
Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:- The present invention relates to a process for the manufacture of pyridones, in particular of compounds which, in one of the possible tautomeric forms, correspond to the formula I
where R is hydrogen or an aliphatic, cyvloaliphatic, araliphatic, aromatic or heterocyclic radical. According to the invention such a compound is manufactured when a compound of the formula II
CH3COCH2CONHR II where R has the above meaning, is reacted with diketene or an acetoacetic acid ester in the presence of a base and in the presence or absence of a solvent.
Examples of suitable bases for use in the reaction with diketene are organic tertiary amines, eg. trialkylamines, dialkylcycloalkylamines, alkyldicycloalkylamines, dialkylaralkylamines, alkyldiaralkylamines, dialkylarylamines and diaralkylarylamines, as well as heterocyclic bases.
Specific examples are trimethylamine, triethylamine, tri-n-propylamine, tributylamine, tri - 2 - ethylhexylamine, N,N - dimethylethylamine, N,N dimethylisopropylamine, N,N - dimethyl - isobutylamine, N,N - dimethyl - 2 ethylhexylamine, N - methylditri - decylamine, N,N,N',N' - tetramethyl - 1,3 diaminopropane, tri - methylenediamine, 1,5 - diazo - bicyclo - [4,3,0] - non 5 - ene, 1,5 - diaza - bicyclo - [5,4,0] - undec - 5 - ene, dimethylcyclohexylamine, ethyldicyclohexylamine, N,N - dimethylbenzylamine, tri - benzylamine, N,N,N',N' - tetramethyl - 4,4' - diamino - diphenyl methane, N,N - dimethylaniline, N,N - diethylaniline, N,N - di - benzylaniline,
N - ethyl - N - benzylaniline, N - ethyl - N - - cyano - ethylaniline, N ethyl - N - benzyl- toluidine, N - p - cyanoethyl - N - acetoxyethyl aniline, N - acetoxyethyl - N - ethylaniline, N,N - dimethyl - m - toluidine, I methylpyrrolidine, I - methylpiperidine, I - ethylpiperidine, 4 methylmorpholine, 4 - ethylmorpholine, I - methylimidazole, 1,2 dimethylimidazole, I - ethylimidazole, I - propylimidazole, pyridine and quinoline.
Particularly suitable solvents for the reaction with diketene are hydrocarbons, chlorohydrocarbons and nitrohydrocarbons, eg. benzene, toluene, xylenes, chlorobenzene, dichlorobenzene, trichloro-benzene, ethylene chloride, methylene chloride, carbon tetrachloride and nitrobenzene.
Advantageous acetoacetic acid esters to use are the methyl and ethyl esters; where these are used, R is advantageously alkyl and particularly hydrogen.
Examples of suitable solvents for the reaction with the acetoacetic acid esters are toluene, xylene, dimethylformamide, N-methylpyrrolidone and especially akanols, eg. methanol, ethanol, propanols and butanols. Examples of suitable bases for the reaction with acetoacetic acid esters are amines, eg.
triethylamine, piperidine and pyrrolidone, sodium hydride, sodium hydroxide, sodium carbonate, potassium carbonate and especially alcoholates. Preferably, the sodium salts or potassium salts of the above alkanols are used, eg. sodium methylate or potassium tert.-butylate.
The reaction according to the invention is advantageously carried out by mixing a compound of the formula TI and a base in a solvent and adding diketene (or the acetoacetic ester) dropwise, with vigorous stirring. Advantageous reaction temperatures are from 50to 150"C, preferably from 100to 130"C, ie. the reaction is preferably carried out under reflux. Advantageously, from 1.1 to 3 moles, preferably from 1.5 to 1.8 moles, of diketene are added per mole or compound 11.
This reaction may be preceded by the preparation of the compounds of the formula II, since these are formed from diketene and an amine of the formula RNH
29 ie. the compounds of the formula I can be prepared by a one-vessel process starting from an amine of the formula RNH2, without the intermediate isolation of the compounds of the formula II.
The bases are in general only added for the reaction of the compounds of the formula II, since the reaction of diketene with the amines of the formula RNH2 to give the compounds of the formula II takes place smoothly even without a catalyst, except in the case of weakly basic aromatic amines. Advantageously, the amount of base used, by weight based on the amount of diketene or acetoacetic acid ester, is from 0.1 to 5%, preferably from 0.2 to 1.5%, in the case of aliphatic bases and from 1 to 50%, preferably about 10%, in the case of aromatic and heterocyclic bases.
The radical R is in particular hydrogen, alkyl of 1 to 8 carbon atoms which is unsubstituted or substituted by alkoxy of I to 4 carbon atoms, cyano, phenoxy, acetoacetoxy, chlorine or bromine, cyclohexyl, phenyl-alkyl (where alkyl is of 1 to 4 carbon atoms), phenyl which is unsubstituted or substituted by chlorine bromine, methyl, ethyl, methoxy, ethoxy or acetylamino, naphthyl, pyridyl, quinaldinyl, benzthiazolyl or pyrazolyl. When R is hydrogen the compounds alternatively exist as 2,6 - dihydroxy - 3 - acetyl - 4 - methylpyridines, as can be seen from the Examples.
Specific examples of R, in addition to hydrogen, are methyl, ethyl, n- and isopropyl, n-butyl, iso-butyl, n-octyl, 2-ethylhexyl, stearyl, 2-methoxyethyl, 2ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3 - (2 ethylhexoxy) - propyl, cyclohexyl, 2-methylcyclohexyl, benzyl, 2 phenylethyl, 2phenylpropyl, 2-dimethylaminoethyl, 3-dimethylaminopropyl, 3diethylaminopropyl, 3-phenoxypropyl, 3 - (2' - phenoxyethoxy) - propyl, benzyloxypropyl, phenyl, 2-chlorophenyl, 2,4 - dichlorophenyl, 2,5dichlorophenyl, 2-methylphenyl, 2,5-dimethylphenyl, 2,4-dimethylphenyl, 2methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,5 - dimethoxy - 4 chlorophenyl, 4 - acetylaminophenyl, I-naphthyl and 8 - (2 - methylquinolinyl).
The process according to the invention is of particular importance for th manufacture of compounds of the formula Ia
where R' is hydrogen, alkyl of I to 4 carbon atoms, alkoxyalkyl (where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 or 3 carbon atoms), cyclohexyl, benzyl, phenylethyl, phenylpropyl or phenyl, which may or may not be substituted by chlorine, methyl or methoxy.
The process using diketene is preferred.
The compounds of the formula I are valuable couplers for the manufacture of dyes, particularly azo dyes.
In the Examples which follow, parts and percentages are by weight, unless stated otherwise.
EXAMPLE 1
210 parts of diketene are added dropwise, at 1 100C, to a mixture of 177 parts of acetoacetic acid anilide and 25 parts of p-cyanoethylethylaniline in 500 parts of xylene. After stirring for 5 hours under reflux, the mixture is allowed to cool and the product is filtered off, washed with xylene and dried. 224 parts of 1 - phenyl 3 - acetyl - 4 - hydroxy - 6 - methyl - 2 - pyridone of melting point 222--226"C.
(literature: 217--218"C) are obtained. The mother liquor is extracted by shaking with a total of 3 liters of saturated sodium bicarbonate solution, employed in 3 portions. The combined alkaline extracts are acidified with concentrated hydrochloric acid. The precipitate is filtered off, dried and purified by recrystallization from methanol. Pure 1 - phenyl - 3 - acetyl - 4 - methyl - 6 hydroxy - 2 - pyridone of the formula
is obtained; it melts at 163--165"C.
C,4HI3NO3 (243)
Calculated C 69.2 H 5.4 N 5.7 0 19.7
Found C 69.0 H 5.6 N 5.7 0 20.0
EXAMPLE 2
If the procedure described in Example 1 is followed but N,N-dimethylaniline is used as the base instead of p-cyanoethylethylaniline, the coupler 1 - phenyl 3 - acetyl - 4 - methyl - 6 - hydroxy - 2 - pyridone is obtained in the same yield and purity.
In the Examples which follow, the procedure described in Example I is followed, but instead of the unsubstituted acetoacetic acid anilide, the acetoacetamides shown in the Table are reacted with diketene, and the stated 3 acetyl - 6 - hydroxy - 2 - pyridones are obtained.
Example No. R 3 Cl Cl 4C1
Example No R C1 5 C1 Cl 6 Cl OCH 7 bug OCH 8 OCH3 9 10 CH3 CH3 0C2H5 11 12 OCH, 12 OCH3 C1 OCH 13 Cl OCH3 CH 14 \2 OCH3 EXAMPLE 15
86 parts of diketene are added dropwise, at 70--800C internal temperature, to 93 parts of aniline in 500 parts of xylene. When no further aniline is detectable by chromatography, 20 parts of N,N-diethylaniline are added, the mixture is heated to 11--1200C, and a further 210 parts of diketene are added dropwise.
After refluxing for 6 hours, the mixture is allowed to cool, the by-product I phenyl - 3 - acetyl - 4 - hydroxy - 6 - methyl - 2 - pyridone is filtered off and the mother liquor is extracted with saturated sodium bicarbonate solution. After acidifying with concentrated hydrochloric acid, filtering off, drying and recrystallizing from methanol, pure I - phenyl - 3 - acetyl - 4 - methyl - 6 hydroxy - 2 - pyridone of melting point 163--165"C is obtained; its coupling number equivalent is 234 (calculated: 243).
EXAMPLE 16
16 parts of N,N-diethylaniline are added to 100 parts of acetoacetamide in 400 parts of toluene. After heating the mixture to 1000C, 126 parts of diketene are added dropwise and the batch is refluxed for 5 hours. When it has cooled, the product is filtered off and, after drying, 100 parts of a mixture of substances containing 86% of 2,6 - dihydroxy - 3 - acetyl - 4 - methyl - pyridine
is obtained.
The pure compound is obtained by stirring the crude product with saturated sodium bicarbonate solution, whereupon the isomeric 2,4 - dihydroxy - 3 acetyl - 6 - methylpyridine remains undissolved (melting point 266-2700C; literature: 2680C). The mother liquor is acidified with concentrated hydrochloric acid and the precipitate is filtered off and dried. Melting point 228--232"C; coupling equivalent 172 (calculated: 167).
C8HgNO3 (167)
Calculated C 57.6 H 5.4 N 8.4 0 28.8
Found C 57.5 H 5.7 N 8.6 0 28.5
In the Examples which follow, the procedure described in Example 16 is employed. The 16 parts of N,N - diethylaniline are replaced by the amounts of other bases shown in the Table, and 2,6 - dihydroxy - 3 - acetyl - 4 methylpyridine is obtained in the yield shown.
bcample Parts of base Parts of No.
CR, ,COCH, 17 27 parts of N,N-dibenzylamine 70.5 18 12- parts of N,N-dimethylaniline 69 19 21 parts of N-ethyl-N-benzylaniline 70.5 20 17.5 parts of -cyanoethylethyl aniline 81 21 0.4 part of triethylamine 39 22 1.8 parts of triethylamine 26 23 8 parts of triethylamine 10 24 10 parts of pyridine 34 25 3 parts of diazabicyclo-[4,3,0] non-5-ene 26 4 parts of triethylenediamine 50 27 8 parts of l-methylimidazole 72 28 10 parts of l-methylmorpholine 68 29 9 parts of 1,2-dimethylimidazole 64 EXAMPLE 30
18 g of ammonia gas are passed into a solution of 84 parts of diketene in 400 parts of toluene whilst cooling with a mixture of solid carbon dioxide and acetone.
After the gas has been introduced, the cooling is removed and the mixture is allowed to come to room temperature. 15 parts of N,N-dimethylaniline are added, the mixture is heated to 75"C and 126 parts of diketene are added dropwise in the course of 30 minutes. After refluxing for 6 hours, the mixture is allowed to cool and is stirred with 2 liters of saturated sodium bicarbonate solution, employed in 2 portions. The phases are separated, the aqueous-alkaline extract is acidified, the product is filtered off and after drying 78 parts of 2,6 - dihydroxy - 3 - acetyl 4 - methylpyridine are obtained; melting point 228-2320C.
EXAMPLE 31
If the procedure described in Example 16 is followed, but chlorobenzene is employed as the solvent, 2,6 - dihydroxy - 3 - acetyl - 4 - methylpyridine is obtained in similar purity and yield.
EXAMPLE 32
If toluene is replaced by xylene as the solvent, and in other respects the procedure described in Example 16 is followed, 2,6 - dihydroxy - 3 - acetyl - 4 methylpyridine is obtained in similar yield and purity.
EXAMPLE 33
If the procedure of Example 16 is followed, but nitro-benzene is employed as the solvent, 2,6 - dihydroxy - 3 - acetyl - 4 - methylpyridine is obtained in similar purity but somewhat lower yield.
EXAMPLE 34
336 parts of diketene are added to 2,000 parts of toluene. 126 parts of monomethylamine are passed in whilst cooling with a mixture of solid carbon dioxide and acetone. When the gas has been introduced, 60 parts of dimethylaniline are added and a further 336 parts of diketene are introduced dropwise at an internal temperature of 670"C. The mixture is heated to the reflux temperature, refluxed for 6 hours and then allowed to cool. The batch is extracted with three times 1.5 liters of saturated sodium bicarbonate solution. The aqueous alkaline phase is then acidified and the precipitate is filtered off, washed neutral and dried. 376 parts of 1,4 - dimethyl - 3 - acetyl - 6 - hydroxy - 2 pyridone of the formula
are obtained, melting at 7-730C (after recrystallization from cyclohexane).
C9H "NO3 (181)
Calculated C59.7 H6.1 N7.7 026.5
Found C 59.9 H6.1 N 7.8026.5 EXAMPLE 35
4 parts of N - ethyl - N - p - cyanoethylaniline are added to 23 parts of Nmethylacetoacetamide in 100 parts of toluene. The mixture is heated to 100"C and 26 parts of diketene are added dropwise. After refluxing for 10 hours, the mixture is allowed to cool and is then extracted by shaking with about 250 ml of saturated sodium carbonate solution. The aqueous phase is acidified with concentrated hydrochloric acid. The oil which separates out crystallizes completely after a short time. This product is filtered off, washed neutral and dried. Yield: 15 parts of 1,4 dimethyl - 3 - acetyl - 6 - hydroxypyrid - 2 - one of the formula
In the Examples which follow, the procedure of Example 35 is employed, but instead of N-methylacetoacetamide the acetoacetic acid amides shown in the
Table are employed and the stated 3 - acetyl - 4 - methyl - 6 - hydroxy - pyrid 2 - ones are obtained.
Example No.
36 -c2M5 37 -C3H7 38 -nC4Hg 39 (CH3)2-CH-CN3 40 -C1{2-C1H-C4H C2H5 41 42 CH3 43 -CH2-C6H5 44 -CH2-CH2-C6115 45 -CH2-CH-C6H5 CH3 46 -OH2-CH2-OCH3 47 -CH2-CH2-0C2H5 48 -CH2-CH2-CH2 oC 3 49 -CH2-CH2-CH2-oC2 5 50 -(CH2)30CH2-pH-C4Hg CR 25
Example No. R 51 -cH2-CH2-N(cH3)2 52 -cH2-CH2-N(C2H5)2 EXAMPLE 53
0.2 part of triethylamine is added to 11.5 parts of N-methylacetoacetamide in 90 parts of toluene. The mixture is heated to 8(850C and a solution of 13 parts of diketene in 40 parts of toluene is then run in over 2 hours. The batch is refluxed for 5 hours, allowed to cool and extracted with saturated sodium carbonate solution. The aqueous alkaline phase is acidified and the precipitate is filtered off, washed neutral and dried. Yield: 5 parts of 1,4 - dimethyl - 3 - acetyl - 6 hydroxy - pyrid - 2 - one.
EXAMPLE 54
If the procedure described in Example 53 is followed, but 1 g of 1methylimidazole is employed as the catalyst instead of triethylamine, 5 parts of 1,4 - dimethyl - 3 - acetyl - 6 - hydroxy - pyrid - 2 - one are obtained.
EXAMPLE 55
198 parts of a 30% strength solution of sodium methylate in methanol are added to 101 parts of acetoacetic acid amide and 143 parts of ethyl acetoacetate in 300 parts of methanol. The mixture is refluxed for 10 hours and about 250 parts of methanol are then distilled off. Water is added to the only residue and the mixture is brought to pH 45 with dilute hydrochloric acid. After filtering off and drying the product, 26 parts of pure 2,6 - dihydroxy - 3 - acetyl - 4 - methyl - pyridine are obtained.
EXAMPLE 56
500 parts of methanol, 151 parts of acetoacetic acid amide, 195 parts of ethyl acetoacetate and 297 parts of 30% strength sodium methyl ate solution are heated in an autoclave for 10 hours at 1200C. The reaction mixture is then concentrated as far as possible under reduced pressure and the pH is brought to 1-2 with dilute hydrochloric acid. The product is filtered off, washed neutral and dried. The yield of 2,6 - dihydroxy - 3 - acetyl - 4 - methylpyridine is 44 parts.
EXAMPLE 57
10 parts of acetoacetamide in 100 parts of dimethylformamide are heated with 14.3 parts of ethyl acetoacetate and 12.3 parts of potassium tert.-butylate for 3 hours at 90--1000C. When the mixture has cooled, 300 parts of water are added, the batch is acidified to pH 1--2, and after filtering off drying about I part of 2,6 dihydroxy - 3 - acetyl - 4 - methyl - pyridine is obtained.
EXAMPLE 58
If the procedure described in Example 57 is followed, but 20 parts of 20% strength aqueous sodium hydroxide solution are employed as the base, the desired pyridine derivative is obtained in similar yield.
EXAMPLE 59
If the procedure described in Example 57 is followed, but Nmethylpyrrolidone is employed as the solvent, and 15 parts of anhydrous potassium carbonate as the base in place of potassium tert.butylate, 2,6 dihydroxy - 3 - acetyl - 4 - methyl - pyridine is again obtained, in about the same yield.
EXAMPLE 60
11.5 parts of N-methylacetoacetamide, 14.3 parts of ethyl acetoacetate and 20 parts of a 30% strength solution of sodium methylate in methanol are refluxed, in 150 parts of methanol, for 10 hours. The solvent is distilled off as completely as possible, water is added to the oily residue and the patch is acidified with acetic acid. After standing overnight at OOC, the product is filtered off, washed neutral and dried. 1.5 parts of 1,4 - dimethyl - 3 - acetyl - 6 - hydroxy - pyrid - 2 - one are obtained.
EXAMPLE 61
11.5 parts of N-methylacetoacetamide, 12 parts of methyl acetoacetate and 12.5 parts of potassium tert.-butylate in 50 parts of ethylene glycol are heated for 6 hours at 800 C. The mixture is allowed to cool and precipitated in water, and the pH is brought to 4--5 with acetic acid. After the mixture has stood overnight at OOC, the product is filtered off and about 1 part of 1,4 - dimethyl - 3 - acetyl - 6 hydroxy - pyrid - 2 - one is obtained.
EXAMPLE 62
If the procedure described in Example 61 is followed, but dimethylformamide is employed as the solvent instead of ethylene glycol, 1,4 - dimethyl - 3 - acetyl 6 - hydroxy - pyrid - 2 - one is obtained in similar yield.
EXAMPLE 63
If instead of N-methylacetoacetamide, N-ethylacetoacetamide is employed and in other respects the procedure described in Example 6 is followed, I ethyl - 3 - acetyl - 4 - methyl - 6 - hydroxy - pyrid - 2 - one is obtained in similar yield.
EXAMPLE 64
16 parts of N - n - butylacetoacetamide, 13 parts of ethyl acetoacetate and 20 parts of a 30% strength solution of sodium methylate in methanol are refluxed in 150 parts of methanol for 10 hours. The solvent is distilled off as completely as possible, water is added to the residue and the mixture is acidified with acetic acid. After standing overnight, the product is filtered off, washed neutral and dried. 2 parts of I - n - butyl - 3 - acetyl - 4 - methyl - 6 - hydroxy - pyrid - 2 one are obtained.
WHAT WE CLAIM IS:- 1. A process for the manufacture of a pyridone which in one of the possible tautomeric forms corresponds to the formula
where R is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical, wherein a compound of the formula CH3COCH2CONHR (II) where R has the above meaning, is reacted with diketene or an acetoacetic acid ester in the presence of a base and in the presence or absence of a solvent.
2. A process as claimed in claim 1 wherein the compound of formula II is reacted with diketene.
3. A process as claimed in claim 2 wherein the base used is an aliphatic base and is used in an amount of from 0.2% to 1.5% by weight, based on diketene.
4. A process as claimed in claim 2 wherein the base used is an aromatic or heterocyclic base and is used in an amount of from 1% to 50% by weight, based on diketene.
5. A process as claimed in any of claims 2 to 4 wherein the compound of formula II is reacted with diketene in the presence of a hydrocarbon, chlorohydrocarbon or nitrobenzene solvent.
6. A process as claimed in any of claims 1 to 5 wherein the compound of formula II has been obtained by reaction of diketene and an amine of the formula RNH2 in which R is as defined in claim 1.
7. A process as claimed in claim 6 carried out as a one-vessel process without intermediate isolation of the compound of the formula II but reacting it in situ with diketene.
8. A process as claimed in claim 1 wherein the compound of formula II is reacted with methyl or ethyl acetoacetate.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (15)
1. A process for the manufacture of a pyridone which in one of the possible tautomeric forms corresponds to the formula
where R is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical, wherein a compound of the formula CH3COCH2CONHR (II) where R has the above meaning, is reacted with diketene or an acetoacetic acid ester in the presence of a base and in the presence or absence of a solvent.
2. A process as claimed in claim 1 wherein the compound of formula II is reacted with diketene.
3. A process as claimed in claim 2 wherein the base used is an aliphatic base and is used in an amount of from 0.2% to 1.5% by weight, based on diketene.
4. A process as claimed in claim 2 wherein the base used is an aromatic or heterocyclic base and is used in an amount of from 1% to 50% by weight, based on diketene.
5. A process as claimed in any of claims 2 to 4 wherein the compound of formula II is reacted with diketene in the presence of a hydrocarbon, chlorohydrocarbon or nitrobenzene solvent.
6. A process as claimed in any of claims 1 to 5 wherein the compound of formula II has been obtained by reaction of diketene and an amine of the formula RNH2 in which R is as defined in claim 1.
7. A process as claimed in claim 6 carried out as a one-vessel process without intermediate isolation of the compound of the formula II but reacting it in situ with diketene.
8. A process as claimed in claim 1 wherein the compound of formula II is reacted with methyl or ethyl acetoacetate.
9. A process as claimed in claim 8 wherein R in the compound of formula ll is
hydrogen or alkyl.
10. A process as claimed in claim 8 or 9 carried out in the presence of an alkanol as solvent using a sodium or potassium alkanolate as the base.
11. A process as claimed in any of claims I to 10 wherein R in formula II is hydrogen, alkyl of I to 8 carbon atoms which is unsubstituted or substituted by alkoxy of I to 4 carbon atoms, cyano, phenoxy, acetoacetoxy, chlorine or bromine, phenylalkyl where alkyl is of 1 to 4 carbon atoms, phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or acetylamino, naphthyl, pyridyl, quinaldinyl, benzthiazolyl or pyrazolyl.
12. A process as claimed in claim 11 wherein R in formula II is hydrogen, alkyl of I to 4 carbon atoms, alkoxyalkyl (where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 or 3 carbon atoms), cyclohexyl, benzyl, phenylethyl, phenylpropyl, phenyl or phenyl substituted by chlorine, methyl or methoxy.
13. A process for the manufacture of a pyridone carried out substantially as hereinbefore described in any one of the Examples.
14. A pyridone as defined in claim 1 whenever obtained by a process as claimed in any preceding claim.
15. An azo dye whenever made using a pyridone as claimed in claim 14 as a coupler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772705562 DE2705562A1 (en) | 1977-02-10 | 1977-02-10 | METHOD FOR MANUFACTURING PYRIDONS |
| DE19772721888 DE2721888A1 (en) | 1977-02-10 | 1977-05-14 | METHOD FOR MANUFACTURING PYRIDONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1593822A true GB1593822A (en) | 1981-07-22 |
Family
ID=25771583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB520578A Expired GB1593822A (en) | 1977-02-10 | 1978-02-09 | Manufacture of pyridones |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5398972A (en) |
| DE (2) | DE2705562A1 (en) |
| GB (1) | GB1593822A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912118A (en) * | 1983-09-23 | 1990-03-27 | National Research Development Corporation | Pharmaceutical compositions |
| US6696552B2 (en) * | 2002-06-27 | 2004-02-24 | Xerox Corporation | Process for preparing substituted pyridone compounds |
| US7141670B2 (en) | 2001-10-15 | 2006-11-28 | Lonza Ltd. | Process for the preparation of 1-(pyrimidin-2-yl)propan-2-ones |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4157446A (en) * | 1976-08-05 | 1979-06-05 | Cassella Aktiengesellschaft | 3-Formyl-pyridines and process for making them |
| US4286091A (en) | 1980-05-19 | 1981-08-25 | Diamond Shamrock Corporation | Synthesis of pyridazinone pharmaceutical intermediates using diketene reactant |
| DE3221948A1 (en) * | 1982-06-11 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | N-ARYLPYRIDONE, THEIR PRODUCTION AND USE |
| GB8325496D0 (en) * | 1983-09-23 | 1983-10-26 | Hider R C | Pharmaceutical compositions |
| USRE34313E (en) * | 1983-09-23 | 1993-07-13 | National Research Development Corporation | Pharmaceutical compositions |
| JP4752740B2 (en) * | 2006-11-27 | 2011-08-17 | パナソニック電工株式会社 | Rotary switch |
| WO2022091001A1 (en) | 2020-10-29 | 2022-05-05 | Pfizer Ireland Pharmaceuticals | Process for preparation of palbociclib |
-
1977
- 1977-02-10 DE DE19772705562 patent/DE2705562A1/en not_active Withdrawn
- 1977-05-14 DE DE19772721888 patent/DE2721888A1/en not_active Withdrawn
-
1978
- 1978-02-09 GB GB520578A patent/GB1593822A/en not_active Expired
- 1978-02-10 JP JP1365278A patent/JPS5398972A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912118A (en) * | 1983-09-23 | 1990-03-27 | National Research Development Corporation | Pharmaceutical compositions |
| US5104865A (en) * | 1983-09-23 | 1992-04-14 | National Research Development Corporation | Iron complexes of hydroxypyridones useful for treating iron overload |
| US7141670B2 (en) | 2001-10-15 | 2006-11-28 | Lonza Ltd. | Process for the preparation of 1-(pyrimidin-2-yl)propan-2-ones |
| US6696552B2 (en) * | 2002-06-27 | 2004-02-24 | Xerox Corporation | Process for preparing substituted pyridone compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2705562A1 (en) | 1978-08-17 |
| DE2721888A1 (en) | 1978-11-23 |
| JPS5398972A (en) | 1978-08-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |