US3890368A - Method for N,N-dicyanoethylating aminophenols - Google Patents
Method for N,N-dicyanoethylating aminophenols Download PDFInfo
- Publication number
- US3890368A US3890368A US372315A US37231573A US3890368A US 3890368 A US3890368 A US 3890368A US 372315 A US372315 A US 372315A US 37231573 A US37231573 A US 37231573A US 3890368 A US3890368 A US 3890368A
- Authority
- US
- United States
- Prior art keywords
- aminophenol
- percent
- acetic acid
- content
- original
- 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 - Lifetime
Links
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 55
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 229960000583 acetic acid Drugs 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007278 cyanoethylation reaction Methods 0.000 description 2
- ZKZPGKMLMRIDJQ-UHFFFAOYSA-N 3-[N-(2-cyanoethyl)-4-hydroxyanilino]propanenitrile Chemical compound OC1=CC=C(C=C1)N(CCC#N)CCC#N ZKZPGKMLMRIDJQ-UHFFFAOYSA-N 0.000 description 1
- HBZUTHNXOTWAFZ-UHFFFAOYSA-N 3-[n-(2-cyanoethyl)-2-hydroxyanilino]propanenitrile Chemical compound OC1=CC=CC=C1N(CCC#N)CCC#N HBZUTHNXOTWAFZ-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Definitions
- these objects are achieved by heating a mixture consisting essentially of an aminophenol, acrylonitrile, and glacial acetic acid at a temperature between about 25C. and the reflux temperature of the mixture.
- a mixture consisting essentially of an aminophenol, acrylonitrile, and glacial acetic acid
- the product may be recovered by quenching the reaction mixture with water provided the acetic acid content does not exceed about 70 percent of the aminophenol content. If excess acetic acid is present, it may be removed by distillation along with unreacted acrylonitrile prior to quenching the reaction mixture.
- the method of the present invention is applicable to p-, or m-aminophenols and to substituted derivatives thereof provided the substituents do not themselves react with acrylonitrile.
- reaction is essentially complete in eight hours, but reflux may be continued overnight or longer without deleterious effect.
- the preparation is convenient as all the reagents are added at once and reflux temperatures are sufficient. No pressure equipment is needed.
- the product is isolated in good yield by simply quenching in water.
- the product is obtained as a light colored solid which may be recrystallized if desired, but the crude material is suitable for further reactions, e.g., hydrolysis to the diacid.
- the products obtained using the present invention are light-colored even when prepared under normal atmospheric conditions although an inert atmosphere (e.g., nitrogen) may be provided if desired.
- an inert atmosphere e.g., nitrogen
- the product may be recrystallized from ethyl acetate or aqueous acetic acid.
- a sample purified by the latter method yielded light yellow needles, mp. -81C.
- N.m.r. and i.r. data confirmed the identity of the product.
- Example I is repeated but o-aminophenol is substituted for the p-aminophenol.
- the product secured was N,N-bis (2-cyanoethyl)-o-aminophenol.
- a method for preparing an N,N-dicyanoethylated aminophenol which comprises heating a mixture consisting essentially of an aminophenol at least 2 mols of acrylonitrile for each mol of the aminophenol, and glav cial acetic acid in an amount at least 50 percent by weight of the aminophenol, at a temperature between about 25C. and the reflux temperature of the mixture, and thereafter quenching the reaction mixture with water to precipitate a substantially pure dicyanoethylated phenol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372315A US3890368A (en) | 1973-06-21 | 1973-06-21 | Method for N,N-dicyanoethylating aminophenols |
| NL7408084A NL7408084A (enrdf_load_stackoverflow) | 1973-06-21 | 1974-06-17 | |
| GB2701374A GB1405243A (en) | 1973-06-21 | 1974-06-18 | Method for n,n-dicyanoethylating aminophenols |
| BE145700A BE816646A (fr) | 1973-06-21 | 1974-06-20 | Procede de n,n-dicyanoethylation d'aminophenols |
| CH844874A CH587232A5 (enrdf_load_stackoverflow) | 1973-06-21 | 1974-06-20 | |
| SE7408179A SE411751B (sv) | 1973-06-21 | 1974-06-20 | Forfarande for framstellning av n,n-dicyanoetylsubstituerade aminofenoler |
| FR7421524A FR2234279B1 (enrdf_load_stackoverflow) | 1973-06-21 | 1974-06-20 | |
| IT51640/74A IT1016121B (it) | 1973-06-21 | 1974-06-20 | Procedimento per la produzione di amminofenoli n.n. dicianoetilati |
| JP49070342A JPS50157324A (enrdf_load_stackoverflow) | 1973-06-21 | 1974-06-21 | |
| DE2429781A DE2429781C2 (de) | 1973-06-21 | 1974-06-21 | Verfahren zur Herstellung von N,N-Bis-(2-cyanoäthyl)-amino-phenolen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372315A US3890368A (en) | 1973-06-21 | 1973-06-21 | Method for N,N-dicyanoethylating aminophenols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3890368A true US3890368A (en) | 1975-06-17 |
Family
ID=23467635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US372315A Expired - Lifetime US3890368A (en) | 1973-06-21 | 1973-06-21 | Method for N,N-dicyanoethylating aminophenols |
Country Status (10)
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2519002C3 (de) * | 1975-04-29 | 1978-09-21 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Herstellung von l-(2-Cyanathylamino)-3-acylaminobenzolen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809983A (en) * | 1956-03-12 | 1957-10-15 | Monsanto Chemicals | Hydroxyanilinopropionitriles |
| US3743668A (en) * | 1971-06-01 | 1973-07-03 | Mallinckrodt Chemical Works | Cyanoethylation of aminophenols |
-
1973
- 1973-06-21 US US372315A patent/US3890368A/en not_active Expired - Lifetime
-
1974
- 1974-06-17 NL NL7408084A patent/NL7408084A/xx not_active Application Discontinuation
- 1974-06-18 GB GB2701374A patent/GB1405243A/en not_active Expired
- 1974-06-20 BE BE145700A patent/BE816646A/xx not_active IP Right Cessation
- 1974-06-20 IT IT51640/74A patent/IT1016121B/it active
- 1974-06-20 CH CH844874A patent/CH587232A5/xx not_active IP Right Cessation
- 1974-06-20 SE SE7408179A patent/SE411751B/xx unknown
- 1974-06-20 FR FR7421524A patent/FR2234279B1/fr not_active Expired
- 1974-06-21 JP JP49070342A patent/JPS50157324A/ja active Pending
- 1974-06-21 DE DE2429781A patent/DE2429781C2/de not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809983A (en) * | 1956-03-12 | 1957-10-15 | Monsanto Chemicals | Hydroxyanilinopropionitriles |
| US3743668A (en) * | 1971-06-01 | 1973-07-03 | Mallinckrodt Chemical Works | Cyanoethylation of aminophenols |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2429781A1 (de) | 1975-01-23 |
| JPS50157324A (enrdf_load_stackoverflow) | 1975-12-19 |
| DE2429781C2 (de) | 1983-10-27 |
| IT1016121B (it) | 1977-05-30 |
| SE411751B (sv) | 1980-02-04 |
| NL7408084A (enrdf_load_stackoverflow) | 1974-12-24 |
| GB1405243A (en) | 1975-09-10 |
| SE7408179L (enrdf_load_stackoverflow) | 1974-12-23 |
| FR2234279B1 (enrdf_load_stackoverflow) | 1978-01-13 |
| CH587232A5 (enrdf_load_stackoverflow) | 1977-04-29 |
| BE816646A (fr) | 1974-12-20 |
| FR2234279A1 (enrdf_load_stackoverflow) | 1975-01-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: MALLINCKRODT, INC. Free format text: CHANGE OF NAME;ASSIGNOR:MALCO, INC.;REEL/FRAME:004572/0403 Effective date: 19860101 Owner name: MALCO, INC., ST. LOUIS, MISSOURI A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MALLINCKRODT, INC.;REEL/FRAME:004572/0411 Effective date: 19860102 |
|
| AS | Assignment |
Owner name: MALLINCKRODT SPECIALTY CHEMICALS COMPANY, A DE COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MALLINCKRODT, INC., A DE CORP.;REEL/FRAME:005602/0024 Effective date: 19901220 |