IL34829A - Process for the production of 3-aminoazacycloheptan-2-one - Google Patents
Process for the production of 3-aminoazacycloheptan-2-oneInfo
- Publication number
- IL34829A IL34829A IL34829A IL3482970A IL34829A IL 34829 A IL34829 A IL 34829A IL 34829 A IL34829 A IL 34829A IL 3482970 A IL3482970 A IL 3482970A IL 34829 A IL34829 A IL 34829A
- Authority
- IL
- Israel
- Prior art keywords
- azacycloheptan
- amino
- nitro
- reduction
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- BOWUOGIPSRVRSJ-UHFFFAOYSA-N 2-aminohexano-6-lactam Chemical compound NC1CCCCNC1=O BOWUOGIPSRVRSJ-UHFFFAOYSA-N 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- MFMLHXQPFVVJNK-UHFFFAOYSA-N 3-nitro-2-oxoazepane-1-carbaldehyde Chemical compound [O-][N+](=O)C1CCCCN(C=O)C1=O MFMLHXQPFVVJNK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 230000000802 nitrating effect Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WQSVMASHWYAHSQ-UHFFFAOYSA-N 1-aminoazepan-2-one Chemical compound NN1CCCCCC1=O WQSVMASHWYAHSQ-UHFFFAOYSA-N 0.000 description 1
- RITJPGRHUQHSST-UHFFFAOYSA-N 3-nitroazepan-2-one Chemical compound [O-][N+](=O)C1CCCCNC1=O RITJPGRHUQHSST-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
- C07D223/12—Nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
-fKBsni p SRT8-i j»8K-3 •na*»,> Process for the production of 3· amino-azacycloheptan-2-one AGMIPA 3. .
The present invention concerns a new process for the production of 3-amino-azacycloheptan-2-one (a-amino- £ -capro- lactam) .
There are a number of methods known for the production of 3-amino-azacycloheptan-2-one (a-amino- £-caprolactam) . The most simple process known previously was the reduction of 3-nitro azacycloheptan.-2-one (o-nitro- £ -caprolactam) with hydrogen in the presence of a catalyst to the corresponding amine compound (cf. Swiss patent No. 375,720). The 3-nitro-azacycloheptan-2- one needed as starting material for this process was obtained from 2-chloro-azacyclo-2, 3-heptene by a process which involved several steps and was thus complicated (cf. British patents Nos. 901,169; 867,268; and 867,269). Furthermore it is known that in certain a-halogenocapronic acids the a-halogen atom can be replaced by an amino group by reaction with ammonia. This reaction was applied to a-halogen- £ -caprolactam, the desired amino compound, as the hydrochloride, as well as other reaction products being obtained (cf. U.S. patent No. 2,876,218).
It has now been found that 3-amino-azacycloheptan-2-one is obtained in good purity and good yields by reducing l-formyl-3-riitro-azacycloheptan-2-one with hydrogen under pressure at tempera tures between 50 and 150°C in the presence of ammonia and a solvent. Suitable solvents which can be used are those which are inert towards the reaction components and in which the 3-amino-azacycloheptan-2-one to be produced is readily soluble. The ready solubility of the reaction product in the solvent makes it ..easier to isolate. In particular, solvents which are miscible with water are used. In this way the liquid phase remains homogeneous during the reduction. Preferred solvents are lower alkanols such as ethanol, methanol, isopropanol as well as mixtures of such alkanols with water.
The reduction of the nitro group can be performed with nascent hydrogen or also with molecular hydrogen. It is preferable to perform the reduction with molecular hydrogen in the presence of a catalyst, for example in the presence of Raney-nickel , Raney- cobalt, platinum, palladium and other suitable metals and metallic compounds .
In the process according to the invention, besides the reduction of the nitro group, the formyl group is split off. The formyl group is taken up by ammonia to form formamide or ammonium formiate. It is preferable to employ the ammonia as a gas, since formamide can be easily removed by destination from the reaction mixture. When concentrated aqueous ammonia solution is used,, the formiate is obtained which is difficult to separate. In order to prevent as much as possible the formation of ammonium formiate, it is advisable to perform. the. reaction in an absolute or practically absolute solvent.
In practice, the procedure is as follows: 1-formyl-3-nitro- azacycloheptan-2-one , ethanol and Raney-nickel are added to a . stainless steel autoclave, and ammonia gas is introduced. Then hydrogen gas is introduced into the autoclave in such a manner that the pressure is at least 20 atmospheres. The pressure may vary greatly and may even be increased to 200 to 300 atmospheres. Correspondingly, the reaction temperatures are in a range of from 50-150°C. Ac temperatures higher than that, the reaction does not follow the desired course. In particular, a temperature range of 50-120°C is used, preferably in. the vicinity of 100°C.
The 1-formyl-3-nitro-azacycloheptan-2-one serving as starting material for the process according to the invention is obtained by reaction the oxime of azacycloheptan-2-one ( -capro-lactam) with a formylating agent based on an N-disubstituted formamide and a halogenating agent and afterwards nitrating the complex compound obtained as intermediate. By this process which is a one-step process, the starting material is obtained in good yields of good purity.
The reduction process according to the invention has, compared with previously known processes, the great advantage of employing as starting material a compound which is easy to pro- . , duce. Since the formyl group can be easily cleaved, . the reduction (hydrogenation) and the cleavage can be performed in one operation. Accordingly it is now possible:to obtain..3-amino-azacycloheptan-r 2-one (a-amino- £ -caprolactam) by technically simple reactions.
The following example illustrates the process according to the invention. The temperatures are' given in degrees centigrade.
Example 50 g of 1-formyl-3-nitro-azacycloheptan-2-one , dissolved in 500 ml of 98% ethanol, and 5 g of Raney-nickel are added to a stainless steel autoclave. 46 g of ammonia gas is introduced . into this suspension at room temperature and', then the pressure is raised with hydrogen to 20 atmospheres. The autoclave is then heated within 1½ hours to 100° and kept for 4 hours at this temperature. The autoclave is then cooled to room temperature and the catalyst is removed from the hydrogenation mixture by filtration. The ethanol is removed from the filtrate by distillation in vacuum. The residue is then fractionated, formamide distilling first at 45-49° /0.04 Torr and then the 3-amino-azacycloheptan-2-one (a-^amino- ί -caprolactam) at 108-109° /0.04 Torr. The yield is 26 g, .80% of the theory.
When the Raney-nickel is replaced by palladium on charcoal as catalyst, 27 g of the desired amine are obtained.
Production of the starting material: 70 g of phosgene are introduced at 10 to 15° to 51.2 g of dimethyl-formamide and 30 ml of chloroform. Then the mixture is treated dropwise at 10 to 20° with a solution of 33.9 g of cyclohexanone oxime in 120 ml of chloroform, kept for 12 hours at room . temperature and then heated for 2 hours at 50 to 60°. The solvent is then removed by distillation in vacuum and the residue is added dropwise at 0 to 10° to a nitrating mixture obtained from 60 ml of concentrated nitric acid and 300 ml of concentrated sulfuric acid. After completion of the addition, the nitrating mixture is poured immediately into ice water, precipitating the nitro compound. The precipitate is separated and washed neutral with water. The resulting 1-formyl-3-nitro-azacycloheptan-2-one , recrystallized from ethanol, has a melting point of 120-122°. The yield is 28.5 g, 51,3% of the theory.
Claims (4)
1. Process for the production of 3-amino-azacycloheptan-2-one, characterized by reducing l-formyl-3-nitro-azacyclo-heptan-2-one with hydrogen under pressure at temperatures bet ween 50 and 150°C in the presence of ammonia and a solvent.
2. Process according to Claim 1, characterized by employ ing solvents that are miscible with water, preferably lower alkanols.
3. Process according to Claims 1 and 2, characterized by performing the reduction in the presence of a catalyst.
4. Process according to Claims 1, 2 and '3, characterized by performing the reduction at a pressure of from 20 to 200 atmospheres.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1011069A CH511853A (en) | 1969-07-02 | 1969-07-02 | Process for the preparation of 3-amino-azacycloheptan-2-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL34829A0 IL34829A0 (en) | 1970-09-17 |
| IL34829A true IL34829A (en) | 1972-12-29 |
Family
ID=4359455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL34829A IL34829A (en) | 1969-07-02 | 1970-07-01 | Process for the production of 3-aminoazacycloheptan-2-one |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE752811A (en) |
| CH (1) | CH511853A (en) |
| DE (1) | DE2032627A1 (en) |
| FR (1) | FR2053969A5 (en) |
| GB (1) | GB1322052A (en) |
| IL (1) | IL34829A (en) |
| NL (1) | NL7009727A (en) |
-
1969
- 1969-07-02 CH CH1011069A patent/CH511853A/en not_active IP Right Cessation
-
1970
- 1970-07-01 DE DE19702032627 patent/DE2032627A1/en active Pending
- 1970-07-01 FR FR7024371A patent/FR2053969A5/fr not_active Expired
- 1970-07-01 IL IL34829A patent/IL34829A/en unknown
- 1970-07-01 GB GB3185270A patent/GB1322052A/en not_active Expired
- 1970-07-01 BE BE752811D patent/BE752811A/en unknown
- 1970-07-01 NL NL7009727A patent/NL7009727A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2032627A1 (en) | 1971-01-14 |
| BE752811A (en) | 1971-01-04 |
| GB1322052A (en) | 1973-07-04 |
| IL34829A0 (en) | 1970-09-17 |
| FR2053969A5 (en) | 1971-04-16 |
| CH511853A (en) | 1971-08-31 |
| NL7009727A (en) | 1971-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH031305B2 (en) | ||
| JPH0470308B2 (en) | ||
| US2784191A (en) | Process for the production of lactams | |
| US5475141A (en) | Process for preparing primary amines from aldehydes | |
| US3996246A (en) | Resolution of racemic pantolactone | |
| JPS62138470A (en) | Manufacture of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- piperidinol | |
| US5410082A (en) | Process for preparing amines | |
| IL34829A (en) | Process for the production of 3-aminoazacycloheptan-2-one | |
| JPS5846501B2 (en) | Diaminonaphthalene Seizouhouhou | |
| EP0397042B1 (en) | Process for the preparation of isoquinoline derivatives | |
| US3687940A (en) | Process for the production of 3-amino-azacycloheptan-2-one | |
| CA1094575A (en) | Benzene-1,3,5-tris-acetoxime and the process for making phloroglucinol therewith | |
| US5026864A (en) | Preparation of 2-chloro-5-aminomethyl-pyridine | |
| US3150185A (en) | Hydrogenation of nitrohaloaromatic compounds | |
| JP2000159706A (en) | Production of hydroxyethylcyclohexanes and hydroxyethylpiperidines | |
| US2130480A (en) | Process of hydrogenating 5-nitrophthalide | |
| SU585809A3 (en) | Method of preparing 2-pirrolidone or its alkyl-substitution derivatives | |
| DE19505933C2 (en) | Process for the preparation of L-aspartyl-D-alanine-N- (thietan-3-yl) amides | |
| US2447419A (en) | Preparation of diphenylacetonitrile | |
| GB1589334A (en) | Process for the preparation of aromatic amines from a, -unsaturated cycloaliphatic ketoximes | |
| De | Facile Beckmann rearrangement of ketoximes mediated by yttrium triflate | |
| FI92586C (en) | New stereoselective hydrogenation process | |
| EP0775693B1 (en) | Process for the preparation of 2-amino-6-chlorophenyl-isopropylsulfide | |
| US3517021A (en) | 4-amino-3-cyanopyridines and methods of preparation | |
| US3481938A (en) | Process for the preparation of piperidine |