CA1042894A - Process for the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline and a related compound - Google Patents
Process for the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline and a related compoundInfo
- Publication number
- CA1042894A CA1042894A CA209,659A CA209659A CA1042894A CA 1042894 A CA1042894 A CA 1042894A CA 209659 A CA209659 A CA 209659A CA 1042894 A CA1042894 A CA 1042894A
- Authority
- CA
- Canada
- Prior art keywords
- acetic acid
- mole
- reaction
- diketene
- dihydro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT
A process for producing 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline by reacting one mole of diketene with one mole of m-phenylene diamine. Also, a process for producing 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amino-quinoline by reacting two moles of diketene with one mole of m-phenylene diamine.
A process for producing 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline by reacting one mole of diketene with one mole of m-phenylene diamine. Also, a process for producing 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amino-quinoline by reacting two moles of diketene with one mole of m-phenylene diamine.
Description
l~gZ8~4 BACKGROUND OF THIS INVENTION
1. Field of This Invention This invention relates to a process for the production - of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline. This invention also relates to a process for the production of 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline.
1. Field of This Invention This invention relates to a process for the production - of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline. This invention also relates to a process for the production of 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline.
2. Prior Art 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline has been produced from m-phenylene diamine and acetoacetic ester by heating at 130C. for 19 hours in an autoclave - a 45 to 60 percent yield resulted (Chemisches Zentralblatt, Vol.
109, (1938), page 4240.) Nowadays acetoacetic acid ester is obtained most economically from diketene.
An object of this invention is the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline or 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline by the reaction of diketene with m-phenylene diamine.
SUMMARY OF THE INVENTION
.
According to the invention, about one mole of diketene can be reacted with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline or about two moles of diketene can be reacted with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline.
The above reactions are carried out at a temperature below 100C., at about or below atmospheric pressure and in the presence of catalytic amounts of acetic acid.
The first embodiment of this invention involves a process for producing 1,2-dihydro-2-oxo-4-methyl-7-amino- ~-quinoline. The process includes reacting about one mole of diketene with about one mole of m-phenylene diamine.
.~ ~;
1~4Z894 The phrase "about one mole" includes the range of 0.9 to 1.1 mole. Preferably one mole of diketene is reacted with one mole of m-phenylene diamine. In such a case, yields of 70-to 80 percent are obtained.
The reaction can be conducted in water in the presence of a catalytic amount of acetic acid. Pre-ferably the amount of acetic acid present is 10 percent by weight of the mixture of water and acetic acid.
109, (1938), page 4240.) Nowadays acetoacetic acid ester is obtained most economically from diketene.
An object of this invention is the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline or 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline by the reaction of diketene with m-phenylene diamine.
SUMMARY OF THE INVENTION
.
According to the invention, about one mole of diketene can be reacted with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline or about two moles of diketene can be reacted with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido quinoline.
The above reactions are carried out at a temperature below 100C., at about or below atmospheric pressure and in the presence of catalytic amounts of acetic acid.
The first embodiment of this invention involves a process for producing 1,2-dihydro-2-oxo-4-methyl-7-amino- ~-quinoline. The process includes reacting about one mole of diketene with about one mole of m-phenylene diamine.
.~ ~;
1~4Z894 The phrase "about one mole" includes the range of 0.9 to 1.1 mole. Preferably one mole of diketene is reacted with one mole of m-phenylene diamine. In such a case, yields of 70-to 80 percent are obtained.
The reaction can be conducted in water in the presence of a catalytic amount of acetic acid. Pre-ferably the amount of acetic acid present is 10 percent by weight of the mixture of water and acetic acid.
- 3 -;&~ ' 1~4Z894 The reaction can be conducted in en organic solvent in the presence of about 5 percent by weight of the mixture of the or~anic solvent and th~ acetic acid. That amount of acetic acid is catalytic to the subject reaction. The starting materials are soluble in the organic solvent. Examples of the organic solvent are methanol, butyl acetate, carbon tetrachloride and toluene.
The reaction can also be conducted in glacial acetic acid.
The reaction is conducted at a temperature below 100C. and at about or below atmospheric pressure. Preferably the reaction temperature is between 60 and 65C. Also, under certain circumstances the reaction can be conducted under reflux (reflux i9 the highest temperature which should normally be used).
This embodiment of this invention allows the production of 7-amino-lepidone directly from diketene (in~tead of through acetoacetic ester) using a process which is carried out at considerably lower temperatures than prior process and without pressure, but with better yields.
The second embodiment of this invention involves a process for producing 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline. The process involves reacting about two moles of diketene with about one m~le of m-phenylene diamine. The phrase "about one mole" includes the range of 0.9 to 1.1 mole and the phrase "about two moles" includes the range of 1.9 to 2.1 moles.
Preferably two moles of diketene is reacted with one mole of m-phenylene diamine. In such a case, better results are obtained. ~-~
The reaction can also be conducted in glacial acetic acid.
The reaction is conducted at a temperature below 100C. and at about or below atmospheric pressure. Preferably the reaction temperature is between 60 and 65C. Also, under certain circumstances the reaction can be conducted under reflux (reflux i9 the highest temperature which should normally be used).
This embodiment of this invention allows the production of 7-amino-lepidone directly from diketene (in~tead of through acetoacetic ester) using a process which is carried out at considerably lower temperatures than prior process and without pressure, but with better yields.
The second embodiment of this invention involves a process for producing 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline. The process involves reacting about two moles of diketene with about one m~le of m-phenylene diamine. The phrase "about one mole" includes the range of 0.9 to 1.1 mole and the phrase "about two moles" includes the range of 1.9 to 2.1 moles.
Preferably two moles of diketene is reacted with one mole of m-phenylene diamine. In such a case, better results are obtained. ~-~
-4-1~42894 The reaction can be conducted in water in the presence of a catalytic amount of acetic acid. Preferably the amount of acetic acid present is 10 percent by weight of the mixture of water and acetic acid.
The reaction can be conducted in an organic solvent in the presence of about 5 percent by weight of the mixture of the .~ , organic solvent and the acetic acid. That amount of acetic acid is catalytic, to the subject reaction. The starting materials are soluble in the organic solvent.
The reaction can also be cor.ducted in glacial acetic acid.
The reaction is conducted at a temperature below 100C.
and at about or below atmospheric pressure. Preferably the reaction temperature is between 60 and 65C. Also, the reaction can be conducted under reflux (reflux is the highest temperature which should normally be used).
,.: .
,; :. .
~,.' . .. .
'.'' ' '':
The reaction can be conducted in an organic solvent in the presence of about 5 percent by weight of the mixture of the .~ , organic solvent and the acetic acid. That amount of acetic acid is catalytic, to the subject reaction. The starting materials are soluble in the organic solvent.
The reaction can also be cor.ducted in glacial acetic acid.
The reaction is conducted at a temperature below 100C.
and at about or below atmospheric pressure. Preferably the reaction temperature is between 60 and 65C. Also, the reaction can be conducted under reflux (reflux is the highest temperature which should normally be used).
,.: .
,; :. .
~,.' . .. .
'.'' ' '':
-5-''" :' " ' .. . .
1~4Z894 DETAILED DESCRIPTION OF THIS INVENTION
1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline is also termed 7-amino-2-oxy-lepidine or 7-amino-lepidone. 7-amino-lepidone is a intermediate from which valuable pharmaceuticals ..~.
are and can be made.
1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline is also termed 7-acetoacetylamino-4-mehhyl-quinolone-(2) or 7-acetoacetylamino-lepidone. 7-acetoacetylamino-lepidone is an intermediate from which special pigments are and can be made-All, parts, ratios, percentages and proportions herein are on a weight basis, unless otherwise stated or obvious to one ordinarily skilled in the art from this disclosure.
This example is the preferred mode of the first embodiment of this invention.
43.2 gm. of at least 98 percent pure 1,3-phenylene diamine (melting point: 60 to 62C) and 100 ml of 10 percent acetic acid are placed in a sù~f~rizing flask equipped with an anchor bolt, reflux coo~e~, dr~pping funnel, ther meter and water bath.
35.2 gm. of diketene were allowed to drip into the reaction mixture over the course of about 20 minutes at room temperature.
The reaction mixture was stirred during the addition. The temperature was allowed to rise with the aid of the reaction heat -to 60 to 65C. After completion of the addition of diketene, the reaction was allowed to continue for another hour at 60 to 65C.
After cooling to about 15C. the resultant precipitate was
1~4Z894 DETAILED DESCRIPTION OF THIS INVENTION
1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline is also termed 7-amino-2-oxy-lepidine or 7-amino-lepidone. 7-amino-lepidone is a intermediate from which valuable pharmaceuticals ..~.
are and can be made.
1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline is also termed 7-acetoacetylamino-4-mehhyl-quinolone-(2) or 7-acetoacetylamino-lepidone. 7-acetoacetylamino-lepidone is an intermediate from which special pigments are and can be made-All, parts, ratios, percentages and proportions herein are on a weight basis, unless otherwise stated or obvious to one ordinarily skilled in the art from this disclosure.
This example is the preferred mode of the first embodiment of this invention.
43.2 gm. of at least 98 percent pure 1,3-phenylene diamine (melting point: 60 to 62C) and 100 ml of 10 percent acetic acid are placed in a sù~f~rizing flask equipped with an anchor bolt, reflux coo~e~, dr~pping funnel, ther meter and water bath.
35.2 gm. of diketene were allowed to drip into the reaction mixture over the course of about 20 minutes at room temperature.
The reaction mixture was stirred during the addition. The temperature was allowed to rise with the aid of the reaction heat -to 60 to 65C. After completion of the addition of diketene, the reaction was allowed to continue for another hour at 60 to 65C.
After cooling to about 15C. the resultant precipitate was
-6- -~42~94 :~:
separated out and dried under vacuum at 60 to 70C until the precipitate reached a constant weight. 49.2 gm. of yellow, disc~lored l,2-dihydro-2-oxo-4-methyl-7-amino-quinoline with a melting point of 268 to 269C were obtained, which corresponded -~
to a yield of 70.7 percent, based on the m-phenylene diamine.
After a single recrystallization from dimethylformamide/H20 (1:1), the product was colorless and had a melting point of 274.6 1:o 2~5.4C. ``
The example was repeated, except that the single 10 recrystallization was done using 50 percent acetic acid. The product was colorless and had a melting point of 274.0 to 274.8C.
This example i9 the preferred mode of the second :" `
embodiment of this invention.
129.6 gm of at least 98 percent pure 1,3-phenylene diamine (melting point: 60 to 62C) and 750 ml of 10 percent acetic acid were placed in a sulfurizing flask, equipped with an anchor bolt, reflux cooler, drip funnel, thermometer and water ;
20 bath. 211.2 gm of diketene were allowed to drip into the reaction mixture over the course of 1.5 hours at room temperature. The reaction was stirred during the addition. The temperature, with the aid of the reaction heat, was allowed to rise to 60 to 65C.
After completion of the addition of diketene, the mixture was `
allowed to continue for another hour at 60 to 65C. and was then cool~td to about 15C, The precipitated product was then ~
separated out and dried udder vacuum at 60 to 70C. until the ~ -1s~4Z894 precipate reached a constant weight. 257 gm. of raw, almost colorless, l,2-dihydro-3-oxo-4-methyl-7-acetoacetamino-quinoline was obtained having a melting point of about 238C. This corresponded to a yield of about 83 percent, based on the m-phenylene diamine. After a single recrystallization from 67 percent acetic acid, the product had a melting point of 246.0 to 247.0C. After one more recrystallization from the diluted acetic acid, the melting point was found not to have changed.
separated out and dried under vacuum at 60 to 70C until the precipitate reached a constant weight. 49.2 gm. of yellow, disc~lored l,2-dihydro-2-oxo-4-methyl-7-amino-quinoline with a melting point of 268 to 269C were obtained, which corresponded -~
to a yield of 70.7 percent, based on the m-phenylene diamine.
After a single recrystallization from dimethylformamide/H20 (1:1), the product was colorless and had a melting point of 274.6 1:o 2~5.4C. ``
The example was repeated, except that the single 10 recrystallization was done using 50 percent acetic acid. The product was colorless and had a melting point of 274.0 to 274.8C.
This example i9 the preferred mode of the second :" `
embodiment of this invention.
129.6 gm of at least 98 percent pure 1,3-phenylene diamine (melting point: 60 to 62C) and 750 ml of 10 percent acetic acid were placed in a sulfurizing flask, equipped with an anchor bolt, reflux cooler, drip funnel, thermometer and water ;
20 bath. 211.2 gm of diketene were allowed to drip into the reaction mixture over the course of 1.5 hours at room temperature. The reaction was stirred during the addition. The temperature, with the aid of the reaction heat, was allowed to rise to 60 to 65C.
After completion of the addition of diketene, the mixture was `
allowed to continue for another hour at 60 to 65C. and was then cool~td to about 15C, The precipitated product was then ~
separated out and dried udder vacuum at 60 to 70C. until the ~ -1s~4Z894 precipate reached a constant weight. 257 gm. of raw, almost colorless, l,2-dihydro-3-oxo-4-methyl-7-acetoacetamino-quinoline was obtained having a melting point of about 238C. This corresponded to a yield of about 83 percent, based on the m-phenylene diamine. After a single recrystallization from 67 percent acetic acid, the product had a melting point of 246.0 to 247.0C. After one more recrystallization from the diluted acetic acid, the melting point was found not to have changed.
Claims (17)
1. The process which comprises reacting diketene with m-phenylene diamine at a temperature below 100°C., at about or below atmospheric pressure and in the presence of catalytic amounts of acetic acid, characterized in that the reactants are reacted in the ratio of about one mole of diketene with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline or in the ratio of about two moles of diketene with about one mole of m-phenylene diamine to produce 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline.
2. The process for producing 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline which comprises reacting about one mole of diketene with about one mole of m-phenylene diamine at a temperature below 100°C., at about or below atmospheric pressure and in the presence of catalytic amounts of acetic acid.
3. The process as described in Claim 2 wherein one mole of said diketene is reacted with one mole of said m-phenylene diamine.
4. The process as described in Claim 2 wherein said reaction is conducted in water.
5. The process as described in Claim 4 wherein the acetic acid is 10 percent by weight of a mixture of water and acetic acid.
6. The process as described in Claim 2 wherein said reaction is conducted in an organic solvent in the presence of about 5 percent by weight of a mixture of the organic solvent and the acetic acid, that amount of acetic acid being catalytic, and the starting materials being soluble in the organic solvent.
7. The process of Claim 2 wherein said reaction is conducted in glacial acetic acid.
8. The process of Claim 2, 3 or 6 wherein said temp-erature is between 60° and 65°C.
9. The process of Claim 2, 3 or 6 wherein said reaction is conducted under reflux.
10. The process for producing 1,2-dihydro-2-oxo-4-methyl-7-acetoacetic acid amido-quinoline which comprises reacting about two moles of diketene with about one mole of m-phenylene diamine at a temperature below 100°C., at about or below atmospheric pressure and in the presence of catalytic amounts of acetic acid.
11. The process as described in Claim 10 wherein two moles of said diketene is reacted with one mole of said m-phenylene diamine.
12. The process as described in Claim 10 wherein said reaction is conducted in water.
13. The process as described in Claim 12 wherein the acetic acid is 10 percent by weight of a mixture of water and acetic acid.
14. The process as described in Claim 11 wherein said reaction is conducted in an organic solvent in the presence of about 5 percent by weight of a mixture of the organic solvent and the acetic acid, that amount of acetic acid being catalytic and the starting materials being soluble in the organic solvent.
15. The process of Claim 11 wherein said reaction is conducted in glacial acetic acid.
16. The process of Claim 10, 11 or 14 wherein said temperature is between 60° and 65°C.
17. The process of Claim 10, 11 or 14 wherein said reaction is conducted under reflux.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1349373A CH577973A5 (en) | 1973-09-20 | 1973-09-20 | 4-Methyl-7-substd.-2(1H)-quinolones prepn. - by reacting 1,3-phenylenediamine with diketene |
| CH1349273A CH572471A5 (en) | 1973-09-20 | 1973-09-20 | 4-Methyl-7-substd.-2(1H)-quinolones prepn. - by reacting 1,3-phenylenediamine with diketene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1042894A true CA1042894A (en) | 1978-11-21 |
Family
ID=25712387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA209,659A Expired CA1042894A (en) | 1973-09-20 | 1974-09-20 | Process for the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline and a related compound |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5058080A (en) |
| AT (1) | AT337184B (en) |
| CA (1) | CA1042894A (en) |
| CS (1) | CS182266B2 (en) |
| DD (1) | DD113536A5 (en) |
| DE (1) | DE2444519C2 (en) |
| FR (1) | FR2244763B1 (en) |
| GB (1) | GB1420530A (en) |
| IT (1) | IT1035085B (en) |
| LU (1) | LU70958A1 (en) |
| NL (1) | NL7412463A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0214864A (en) * | 2001-12-11 | 2004-12-14 | Ciba Sc Holding Ag | Process for the preparation of 4-methyl-7-aminoquinolones |
-
1974
- 1974-09-12 JP JP10590474A patent/JPS5058080A/ja active Pending
- 1974-09-13 GB GB4001374A patent/GB1420530A/en not_active Expired
- 1974-09-16 CS CS633874A patent/CS182266B2/en unknown
- 1974-09-18 DE DE19742444519 patent/DE2444519C2/en not_active Expired
- 1974-09-18 IT IT5307374A patent/IT1035085B/en active
- 1974-09-18 DD DD18117974A patent/DD113536A5/xx unknown
- 1974-09-20 AT AT759274A patent/AT337184B/en not_active IP Right Cessation
- 1974-09-20 NL NL7412463A patent/NL7412463A/en not_active Application Discontinuation
- 1974-09-20 FR FR7431844A patent/FR2244763B1/fr not_active Expired
- 1974-09-20 LU LU70958A patent/LU70958A1/xx unknown
- 1974-09-20 CA CA209,659A patent/CA1042894A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA759274A (en) | 1976-10-15 |
| NL7412463A (en) | 1975-03-24 |
| FR2244763B1 (en) | 1979-03-16 |
| CS182266B2 (en) | 1978-04-28 |
| JPS5058080A (en) | 1975-05-20 |
| GB1420530A (en) | 1976-01-07 |
| DE2444519A1 (en) | 1975-03-27 |
| AT337184B (en) | 1977-06-10 |
| FR2244763A1 (en) | 1975-04-18 |
| DD113536A5 (en) | 1975-06-12 |
| DE2444519C2 (en) | 1982-08-26 |
| IT1035085B (en) | 1979-10-20 |
| LU70958A1 (en) | 1975-05-28 |
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