US2709179A - Production of cycloalkanone oximes by the reduction of cyclic nitro paraffins - Google Patents
Production of cycloalkanone oximes by the reduction of cyclic nitro paraffins Download PDFInfo
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- US2709179A US2709179A US217691A US21769151A US2709179A US 2709179 A US2709179 A US 2709179A US 217691 A US217691 A US 217691A US 21769151 A US21769151 A US 21769151A US 2709179 A US2709179 A US 2709179A
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- reduction
- solution
- sulfide
- production
- oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- This invention relates to the production of cycloalkanone oximes by the reduction of cyclic nitro paraffins.
- R1 is an organic radical and R2 is an organic radical or hydrogen.
- This type of reaction can be partly attained by reducing the sodium compound of the nitro parafiin with tin or zinc in an acid medium, preferably by means of hydrochloric acid.
- an acid medium preferably by means of hydrochloric acid.
- Oximes can also be manufactured by reducing sodium salts of nitro paraffins with hydroxylamine compounds, but in this case, the reduction must be carried out at a low temperature, below 5 C., so that intensive cooling is necessary, and the reducing agent is expensive.
- nitrocycloalkanones using a solution of an inorganic sulfide as the reducing agent.
- the nitrocycloalkane such as nitrocyclohexane
- a solvent such as a lower aliphatic alcohol
- a solution of inorganic sulfide is added or formed in situ, by the introduction of materials to form an inorganic sulfide, e. g., by the introduction of ammonia and hydrogen sulfide.
- Example I At a temperature of about 100 C. and in the absence of air, 2 gram moles of sodium hydrosultide are added with moderate stirring to a solution of 1 gram mole of nitrocyclohexane in 2 litres of butanol. After a reaction period of 20 minutes, 55% by weight of the nitrocyclohexane is reduced. The yield of recovered oxime amounts to based on converted nitrocyclohexaue.
- Example I In an analogous manner as described in Example I, the reduction is carried out with ammonium polysulfide at a temperature of 70 C., while ethanol is used as a solvent. The yield of oxime corresponds to 95 of the converted initial material.
- Example III Into a solution of nitrocyclohexane in ethanol containing 0.1 gram mole of nitro compound per litre, equimolecular amounts of ammonia and hydrogen sulfide are introduced at room temperature. After a reaction period of about 1 hour, 95% of the nitrocyclchexane is reduced to the corresponding oxime.
- the reducing agents employed in the process are soluble, inorganic sulfides, such as the neutral or acid sulfides of the alkali metals, the alkaline earth metals and ammonia. Likewise, the polysulfides of these metals or of ammonia may be used.
- the sulfide employed as a reducing agent may be added in a dissolved condition to the nitro compound to be reduced. It is also possible to dissolve the nitro compound in the solvent and to add the sulfide to the resulting solution. Furthermore, the nitro compound may be emulsified in the sulfide solution.
- equimolecular amounts of hydrogen sulfide and ammonia are passed into an alcoholic solution of the nitro compound in which case the sulfide reducing agent is formed in the reaction mixture. It is also pos sible to introduce H28 into a solution of nitrocyclohexane and alkali hydroxide or alkaline earth hydroxide.
- the sulfides are employed as a solution preferably in an organic solvent, especially, a lower aliphatic alcohol, e. g., ethyl alcohol, propyl alcohol, or butyl alcohol, but other solvents, such as water, may be used.
- a lower aliphatic alcohol e. g., ethyl alcohol, propyl alcohol, or butyl alcohol
- solvents such as water
- the proportions of solvent to the reducing agent or, in turn, to the nitrocycloalkane are not critical and ratios of 1 to parts of solvent for each part of sulfide, and 1 to parts of solvent for each part by Weight of nitrocycloalkane are representative of preferred ratios.
- the reaction is carried out at ordinary pressure, since this eliminates the need for complicated apparatus and because the reaction proceeds with very favorable results at these pressures.
- the reaction out at a temperature above the boiling point of the solvent, elevated pressure may be used or suitable condensing apparatus may be employed. It is desirable to carry out the reduction under non-oxidizing conditions in order to avoid oxidation of sulfides, so that a slight over-pressure may conveniently be maintained in the apparatus by means of nitrogen.
- the reduction can proceed satisfactorily at room temperature, i. e., about 15 C., but if more rapid reaction is required, this can be obtained by operating at higher temperatures, for example, 50 to 150 C., making the preferred temperature range between 15 and 150 C. At these temperatures, the reaction time usually is between 10 and 120 minutes, especially 10 to 60 minutes.
- proportions of sulfide to nitrocycloalkane are not critical and may be varied, although for most desirable results stoichiometric proportions of sulfide or a slight excess thereof, for example, between 2 and 3 moles of sulfide for each mole of nitrocycloalkane, are employed.
- any known method can be employed for this purpose, such as extraction of the solution with a preferential solvent for the oxime, precipitation of the oxime by addition of incompatible materials, or by evaporation of these solvents subsequent to removal of undesired nonvolatile components from the reaction liquors.
- a process for the production of cycloalkanone oximcs the step which comprises reducing a. nitrocyclo- If it is desired to carry alkane with a solution of an inorganic salt of hydrogen sulfide in an inert saturated, lower aliphatic alcohol.
- a process for the production of cycloalkanone oximes the step which comprises reducing a nitrocycloalkane with a water solution of an inorganic salt of by drogcn sulfide.
- a process for the production of a cycloalkanone oxime which comprises providing a solution of a nitro cycloalkane in an inert saturated, lower aliphatic alcohol, introducing ammonia and hydrogen sulfide into said solution and continuing said gas introduction until said nitrocycloalkane is substantially completely reduced to a corresponding oxime.
- a process for the production of a cycloalkanone oxime which comprises providing a solution of a nitrocycioalkane in an inert saturated, lower aliphatic alcohol, introducing an inorganic sulfide from the group consisting of alkali metal, alkaline earth metal and ammonium sulfides therein, allowing the admixed material to react at 15 to 150 C. for about it) to 120 minutes and recovering a cycloalkanone oxime from the reaction mixture.
- a process for the production of cyclohexanone oxime which comprises forming a solution of nitrocyclohexane in an inert saturated lower: aliphatic alcohol, heating the solution to about to 0, adding about 2 moles of an inorganic salt or" hydrogen sulfide for each mole of nitrocyclohexane to said solution, allowing the materials to react for about 10 to 60 minutes, and recovering cyclohexanone oxime from the reaction mixture.
Description
United States Patent PRODUCTION OF CYCLOALKANONE OXIMES BY 511% REDUCTION OF CYCLIC NITRO PARAF- Johannes H. Ottenheym, Sittard, Netherlands, assignor to De Directie van de Staatsmijnen in Limburg, handelend voor en namens dc Staat der Nederlanden, Heerlen, Netherlands No Drawing. Application March 26, 1951, Serial No. 217,691
Claims priority, application Netherlands March 31, 1950 10 Claims. (Cl. 260--566) This invention relates to the production of cycloalkanone oximes by the reduction of cyclic nitro paraffins.
FIELD OF INVENTION Many processes are known for the reduction of nitro compounds in which amines are obtained. If it is desired to manufacture oximes from the nitro compounds, the reduction process must be carried out in such a maunor that oxime is formed as an intermediate reduction product which, under the given. reaction conditions, cannot be reduced further to an amine. The reactions involved are represented by the following formula:
wherein R1 is an organic radical and R2 is an organic radical or hydrogen.
This type of reaction can be partly attained by reducing the sodium compound of the nitro parafiin with tin or zinc in an acid medium, preferably by means of hydrochloric acid. However, when such a reduction is carried out, only low yields of oxime, about 40 to 50% by weight based on the nitro compound, are obtained, amines and ketones being formed as by-products.
Oximes can also be manufactured by reducing sodium salts of nitro paraffins with hydroxylamine compounds, but in this case, the reduction must be carried out at a low temperature, below 5 C., so that intensive cooling is necessary, and the reducing agent is expensive.
OBJECTS (2) The provision of new reducing reagents for use in such reactions.
(3) The provision of such reactions which may be carried out at normal temperatures and pressures, thus eliminating need for complex cooling or other complicated apparatus.
(4) The provision of new methods for making cycloalkanone oximes in which the oximes may be produced in relatively high yields.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the 2,799,179 Patented May 24, 1955 spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
GENERAL DESCRIPTION These objects are accomplished according to the present invention through the reduction of nitrocycloalkanones using a solution of an inorganic sulfide as the reducing agent. Preferably, the nitrocycloalkane, such as nitrocyclohexane, is dissolved in a solvent, such as a lower aliphatic alcohol, to which a solution of inorganic sulfide is added or formed in situ, by the introduction of materials to form an inorganic sulfide, e. g., by the introduction of ammonia and hydrogen sulfide.
The success of this invention is due, to a large extent, to the surprising discovery that reduction of nitrocycloalkanes with soluble sulfides leads to the formation of high yields of oximes. This is unique, because the formation of amines, instead of oximes, is to be expected, since it is established practice to employ soluble sulfides as reducing agents in the manufacture of amines from the corresponding aromatic nitro compounds,
The manner in which these new discoveries can be utilized and the details of operation, according to the present invention, can be more fully comprehended by reference to the following illustrative examples of actual operations, in accordance with the invention.
Example I At a temperature of about 100 C. and in the absence of air, 2 gram moles of sodium hydrosultide are added with moderate stirring to a solution of 1 gram mole of nitrocyclohexane in 2 litres of butanol. After a reaction period of 20 minutes, 55% by weight of the nitrocyclohexane is reduced. The yield of recovered oxime amounts to based on converted nitrocyclohexaue.
Example I] In an analogous manner as described in Example I, the reduction is carried out with ammonium polysulfide at a temperature of 70 C., while ethanol is used as a solvent. The yield of oxime corresponds to 95 of the converted initial material.
Example III Into a solution of nitrocyclohexane in ethanol containing 0.1 gram mole of nitro compound per litre, equimolecular amounts of ammonia and hydrogen sulfide are introduced at room temperature. After a reaction period of about 1 hour, 95% of the nitrocyclchexane is reduced to the corresponding oxime.
DETAILED DESCRIPTION The new procedures are generally applicable to nitrocycloalkanes (also called cyclo nitro paraflins). The examples illustrate the use of nitrocyclohexane for this purpose, but other usable materials include:
Nitrocyclopropane Nitro-2,5-dimethyl cyclohexane Nitro-Z-methyl cyclohexane Nitro-4-isopropyl cyclohexane Nitrocyclopentane Nitro-Z-methyl cyclopentane The reducing agents employed in the process are soluble, inorganic sulfides, such as the neutral or acid sulfides of the alkali metals, the alkaline earth metals and ammonia. Likewise, the polysulfides of these metals or of ammonia may be used.
The sulfide employed as a reducing agent may be added in a dissolved condition to the nitro compound to be reduced. It is also possible to dissolve the nitro compound in the solvent and to add the sulfide to the resulting solution. Furthermore, the nitro compound may be emulsified in the sulfide solution.
According to the preferred embodiment, equimolecular amounts of hydrogen sulfide and ammonia are passed into an alcoholic solution of the nitro compound in which case the sulfide reducing agent is formed in the reaction mixture. It is also pos sible to introduce H28 into a solution of nitrocyclohexane and alkali hydroxide or alkaline earth hydroxide.
The sulfides are employed as a solution preferably in an organic solvent, especially, a lower aliphatic alcohol, e. g., ethyl alcohol, propyl alcohol, or butyl alcohol, but other solvents, such as water, may be used. The proportions of solvent to the reducing agent or, in turn, to the nitrocycloalkane are not critical and ratios of 1 to parts of solvent for each part of sulfide, and 1 to parts of solvent for each part by Weight of nitrocycloalkane are representative of preferred ratios.
Preferably, the reaction is carried out at ordinary pressure, since this eliminates the need for complicated apparatus and because the reaction proceeds with very favorable results at these pressures. the reaction out at a temperature above the boiling point of the solvent, elevated pressure may be used or suitable condensing apparatus may be employed. it is desirable to carry out the reduction under non-oxidizing conditions in order to avoid oxidation of sulfides, so that a slight over-pressure may conveniently be maintained in the apparatus by means of nitrogen.
The reduction can proceed satisfactorily at room temperature, i. e., about 15 C., but if more rapid reaction is required, this can be obtained by operating at higher temperatures, for example, 50 to 150 C., making the preferred temperature range between 15 and 150 C. At these temperatures, the reaction time usually is between 10 and 120 minutes, especially 10 to 60 minutes.
The proportions of sulfide to nitrocycloalkane are not critical and may be varied, although for most desirable results stoichiometric proportions of sulfide or a slight excess thereof, for example, between 2 and 3 moles of sulfide for each mole of nitrocycloalkane, are employed.
Although it is possible for some purposes to use the resulting solutions containing the oxime products with out separation of the oxime therefrom, it is generally desirable or necessary to recover the oximc from the reaction liquors. Any known method can be employed for this purpose, such as extraction of the solution with a preferential solvent for the oxime, precipitation of the oxime by addition of incompatible materials, or by evaporation of these solvents subsequent to removal of undesired nonvolatile components from the reaction liquors.
CONCLUSION A new method for making oximes from the corresponding nitrocycloalkanes in high yields and in an easily conducted manner has been described. The reaction has wide application and may be employed to produce a large variety or" oximes of cycloalkanes.
I claim:
1. in a process for the production of cycloalkanone oximes, the step which comprises reducing a nitrocycloalkane with a solution of an inorganic salt of hydrogcn sulfide in an inert solvent.
2. In a process for the production of cycloalkanone oximcs, the step which comprises reducing a. nitrocyclo- If it is desired to carry alkane with a solution of an inorganic salt of hydrogen sulfide in an inert saturated, lower aliphatic alcohol.
3. In a process for the production of cycloalkanone oximes, the step which comprises reducing a nitrocycloalkane with a water solution of an inorganic salt of by drogcn sulfide.
4. A process as claimed in claim 1, wherein said reaction is conducted at a temperature between 15 and 150 C.
5. A process for the production of a cycloalkanone oxime which comprises providing a solution of a nitro cycloalkane in an inert saturated, lower aliphatic alcohol, introducing ammonia and hydrogen sulfide into said solution and continuing said gas introduction until said nitrocycloalkane is substantially completely reduced to a corresponding oxime.
6. A process for the production of a cycloalkanone oxime which comprises providing a solution of a nitrocycioalkane in an inert saturated, lower aliphatic alcohol, introducing an inorganic sulfide from the group consisting of alkali metal, alkaline earth metal and ammonium sulfides therein, allowing the admixed material to react at 15 to 150 C. for about it) to 120 minutes and recovering a cycloalkanone oxime from the reaction mixture.
7. A process as claimed in claim 6, wherein said inorganic sulfide is introduced into said solution by adding hydrogen sulfide and a member of the group consisting of the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and ammonia to the solution.
8. A process for the production of cyclohexanone oxime which comprises forming a solution of nitrocyclohexane in an inert saturated lower: aliphatic alcohol, heating the solution to about to 0, adding about 2 moles of an inorganic salt or" hydrogen sulfide for each mole of nitrocyclohexane to said solution, allowing the materials to react for about 10 to 60 minutes, and recovering cyclohexanone oxime from the reaction mixture.
9. A process as claimed in claim 8, wherein said alcohol is butanol and. said sulfide is sodium hydrosulfide.
10. A process as claimed in claim 8, wherein said alcohol is ethanol and said sulfide is ammonium polysulfide.
References Cited in the file of this patent UNITED STATES PATENTS Fieser and Fieser, Organic Chemistry, 2nd ed., 1950, D. C. Heath and (10., Boston, Mass, pp 617 and 634. Hartman et al., Organic Syntheses, vol. 25, 1945, pp. 5-7.
Claims (1)
1. IN A PROCESS FOR THE PRODUCTION OF CYCLOALKANONE OXIMES, THE STEP WHICH COMPRISES REDUCING A NITROCYCLOALKANE WITH A SOLUTION OF AN INORGANIC SALT OF HYDROGEN SULFIDE IN AN INERT SOLVENT.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2709179X | 1950-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2709179A true US2709179A (en) | 1955-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US217691A Expired - Lifetime US2709179A (en) | 1950-03-31 | 1951-03-26 | Production of cycloalkanone oximes by the reduction of cyclic nitro paraffins |
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| Country | Link |
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| US (1) | US2709179A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2762844A (en) * | 1954-01-28 | 1956-09-11 | Stamicarbon | Preparation of oximes from cycloaliphatic nitrocompounds |
| DE1010067B (en) * | 1955-12-03 | 1957-06-13 | Dr Eugen Mueller | Process for the conversion of secondary aliphatic or cycloaliphatic bis-nitrosocarbons into oximes |
| US3048634A (en) * | 1954-03-30 | 1962-08-07 | Mueller Eugen | Production of ketoximes |
| US3480672A (en) * | 1967-03-28 | 1969-11-25 | Olin Mathieson | Process for reduction of nitro compounds to corresponding oximes and ketones |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE499518A (en) * | ||||
| US2233823A (en) * | 1939-11-15 | 1941-03-04 | Purdue Research Foundation | Process for the reduction of arylnitroalkenes |
| US2423180A (en) * | 1944-03-14 | 1947-07-01 | Union Oil Co | Process for the reduction of nitronaphthenes |
| DE825544C (en) * | 1949-12-01 | 1951-12-20 | Bayer Ag | Process for the preparation of oximes |
| US2696505A (en) * | 1949-11-30 | 1954-12-07 | Bayer Ag | Production of oximes |
-
1951
- 1951-03-26 US US217691A patent/US2709179A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE499518A (en) * | ||||
| US2233823A (en) * | 1939-11-15 | 1941-03-04 | Purdue Research Foundation | Process for the reduction of arylnitroalkenes |
| US2423180A (en) * | 1944-03-14 | 1947-07-01 | Union Oil Co | Process for the reduction of nitronaphthenes |
| US2696505A (en) * | 1949-11-30 | 1954-12-07 | Bayer Ag | Production of oximes |
| DE825544C (en) * | 1949-12-01 | 1951-12-20 | Bayer Ag | Process for the preparation of oximes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2762844A (en) * | 1954-01-28 | 1956-09-11 | Stamicarbon | Preparation of oximes from cycloaliphatic nitrocompounds |
| US3048634A (en) * | 1954-03-30 | 1962-08-07 | Mueller Eugen | Production of ketoximes |
| DE1010067B (en) * | 1955-12-03 | 1957-06-13 | Dr Eugen Mueller | Process for the conversion of secondary aliphatic or cycloaliphatic bis-nitrosocarbons into oximes |
| US3480672A (en) * | 1967-03-28 | 1969-11-25 | Olin Mathieson | Process for reduction of nitro compounds to corresponding oximes and ketones |
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