US3320143A - Process for nitrosation of hydrocarbons - Google Patents

Process for nitrosation of hydrocarbons Download PDF

Info

Publication number
US3320143A
US3320143A US279323A US27932363A US3320143A US 3320143 A US3320143 A US 3320143A US 279323 A US279323 A US 279323A US 27932363 A US27932363 A US 27932363A US 3320143 A US3320143 A US 3320143A
Authority
US
United States
Prior art keywords
nitrosation
hydrocarbon
respect
per
reaction
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
Application number
US279323A
Other languages
English (en)
Inventor
Baumgartner Pierre
Roux-Guerraz Claude
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Application granted granted Critical
Publication of US3320143A publication Critical patent/US3320143A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • This invention relates to a photochemical process for the nitrosation of hydrocarbons, particularly of alkanes and cycloalkancs.
  • the resulting reacted mixture is contacted with an aqueous solution of a strong mineral acid either inside or completely outside the irradiation zone, or both.
  • a strong mineral acid either inside or completely outside the irradiation zone, or both.
  • the solution of the oxime in the strong mineral acid may be neutralized in order to separate therefrom the oxirne or salts thereof. It may also be directly subjected to the Beckmann rearran ement by mere heating, where by the corresponding amide or lactame is obtained,
  • Rh is the average hydraulic radius, i.e., in the case of a reaction vessel having an annular cross-section wherein D is the average external radius in centimeters of the reaction zone and d is the average internal radius in centimeters of the reaction zone;
  • G is the weight of reaction mixture flowing through the reaction zone per unit of time and of area, expressed in grams per sq. centimeter and per second;
  • a is the viscosity of the reaction mixture, expressed in poises.
  • the Reynolds Number should preferably be higher than 1,000. the preferred values being comprised between 5,000 and 50,000.
  • the reaction product may be advantageously extracted substantially as it is formed and for example less than 1 minute and preferably less than 10 seconds after being withdrawn from the reaction zone.
  • the particular nitrosation agent of this invention is not of the essence thereof, but it is preferably a nitrosyl halide, particularly nitrosyi chloride, bromide or fluoride, although there may be used mixtures of halides with at least one nitrogen oxide such as nitric oxide, nitrous anhydride, or nitrogen peroxide.
  • the nitrosyl halide may optionally be formed in situ by means of any convenient reaction therefor.
  • the strong acid may be, for instance, from the group consisting of sulfuric acid, phosphoric acid, and hydrochloric acid.
  • the concentration of the aqueous sulfuric acid solution is highly important and has to be kept Within the range of from 50 to 90% by weight, and preferably between 60 and Otherwise, there will be a considerable decrease in the yield, particularly with respect to the nitrosation agent, and of the output capacity, as well as a rapid deactivation.
  • the step of contacting the reaction mixture with the strong mineral acid must be conducted outside of the irradiation zone, or substantially outside, i.e., at least in a zone where the irradiation intensity is very small as compared to that prevailing in the main irradiation Zone, and corresponds, for instance, to less than 10% of the latter.
  • the reaction is preferably carried out in the presence of a gaseous hydrogen halide, such as, for instance, hydrogen chloride.
  • a gaseous hydrogen halide such as, for instance, hydrogen chloride.
  • gaseous halogen acid is unnecessary.
  • the strong acid is to be used in preferable amounts, for instance, of 0.1 to 10 mols per nitrogen atom of the oxime obtained.
  • the reaction temperature will be advantageously kept in the range of from l0 to 40 C. and preferably be tween 5 and 15 C.
  • the liquid phase reaction mixture may consist only of the treated hydrocarbon together with the nitrosation agent, it may also contain a solvent substantially inert with respect to the nitrosation agent, particularly benzene, carbon tetrachloride or other chlorinated hydrocarbon solvents.
  • a solvent substantially inert with respect to the nitrosation agent particularly benzene, carbon tetrachloride or other chlorinated hydrocarbon solvents.
  • the use of such a solvent is practically necessary where the treated hydrocarbons are normally in a solid state (case for instance of the cyclododecane) in order to avoid the use of excessively high reaction temperatures.
  • too dilute solutions of the hydrocarbon in the solvent for example concentrations lower than 2% by weight, should preferably be avoided.
  • actinic light there is meant radiant energy having a wave length lower than about 7,500 A.
  • source of actinic light there may be used, for instance, a mercury vapor lamp or a sodium vapor lamp.
  • the preferred Wave length range is about 3,000-6,000 A.
  • This process is applicable to alkanes and cycloalkanes, more particularly to the latter, and especially to those containing at least 5, and preferably from to 12 carbon atoms, such as heptane, cyclopentane, hexane, cyclohexane, octane, cyclooctane, dode-cane, and cyclododecane. It is to be understood, however, that this process is also applicable to alkanes and cycloalkanes having less than 5, and more than 12, carbon atoms.
  • Example 1 There is used an apparatus comprising a central glass tube of a 70 cm. length having coaxially placed therein a tubular high pressure mercury vapor lamp of a 60 cm. useful length and a 2 kw. power. Cooling water is passed through said tube to prevent overheating.
  • the reaction mixture is circulated through a space formed between said tube and an external coaxial tube of a larger diameter, surrounding the same.
  • the cross-section of pas-sage for the reaction mixture is bout 3 dm. the useful volume of the rection zone being about 18 liters.
  • reaction mixture is passed through a heat exchanger, and thereafter into a zone for absorption with 70% by weight sulfuric acid.
  • the hydrocarbon mixture is recycled to the inlet of the reaction zone by a pump.
  • the total capacity of the system is about 41 liters. There are initially introduced 40 liters of a mixture of cyclohexane with benzene having a 95% cyclohexane and a 5% benzene content, and to which is added 1% by weight of nitrosyl chloride, where as 1 liter of 70% by weight sulfuric acid is introduced into the absorption zone.
  • This mixture is circulated by means of a pump so as to obtain in the reaction zone an average linear velocity of 0.5 cm. per second which corresponds to anaverage residence time of the cyclohexane in the reaction zone of 120 seconds.
  • the Reynolds Number is about 1,500.
  • the lamp is then illuminated, and the temperature at the inlet of the reaction zone is maintained at about C.
  • Example 2 Example 2 is repeated except that the average velocity of the reactants into the reaction zone is brought to 5 cm. per second, which corresponds to an average residence time of 12 seconds, the other conditions being unchanged.
  • the Reynolds Number is about 15,000.
  • the cyclohexanone-oxime yield is 332 g., an increase of 48% as compared to Example 1, which increased yield is clearly attributable to the increased linear velocity.
  • the molar yields are 75.5%, with respect to nitrosyl chloride, and 84.5% with respect to cyclohexane.
  • Example 3 Example 2 is repeated except that the sulfuric acid solution is replaced by an aqueous solution of hydrochloric acid saturated at a temperature of 25 C.
  • the cyclohexanone-oxime production amounts to 325 g. after one hour.
  • the molar yields are 74.9% wit-h respect to nitrosyl chloride and 84% with respect to cyclohexane.
  • Example 4 Example 2 is repeated, but in the absence of benzene.
  • the cyclohexanone-oxime production amounts to 322 g. after one hour.
  • the molar yields are 75.1% With respect to nitrosyl chloride and 85.2% with respect to cyclohexane.
  • Example 5 Example 2 is repeated, except that an average linear velocity of 1 cm. per second is employed. The cyclohexanone-oxime production amounts to 280 g. after one hours. The molar yields remain unchanged.
  • Example 6 Example 2 is repeated, except that an average linear velocity of 20 cm. per second is employed. The cyclohexanoneoxime production amounts to 340 g. after one hour. The molar yields are unchanged.
  • Example 7 There is used an irradiated vessel of annular cross-section having a useful volume of 2 l. and a useful crosssection area of 40 cm. the lamp being an elongated high pressure mercury vapor lamp of a 700 W. power.
  • This mixture is circulated at an average linear velocity of 1 cm./sec., a Reynolds Number of about 1,800 and a temperature of 5 C.
  • the concentration of nitrosyl chloride is kept constant (1% by Weight) during the reaction.
  • the molar yields are of 76% with respect to nitrosyl chloride and 84% with respect to hexane.
  • Example 8 Example 7 is repeated, except that the average linear velocity is 10 cm./sec. and the Reynolds Number is 18,000. After one hour, 40 g. of the same oil as in Example 7 have been obtained. The molar yields remain unchanged.
  • Example 9 Example 7 is repeated, except that hexane is replaced by heptane.
  • the oxime as a viscous oil 5
  • the molar yield is 74% with respect to nitrosyl chloride and 85% with respect to heptane.
  • Example 10 Example 9 is repeated, except that the average linear velocity is 10 cm./sec. and the Reynolds Number is 18,000.
  • Example 9 After one hour, 46 g. of the same oil as in Example 9 have been obtained. The molar yields are the same as in Example 9.
  • Example 11 Example 12 Example 11 is repeated, except that the average linear velocity is 1-0 cm./ sec. and the Reynolds Number is 13,000.
  • the amount of cyclododecanone-oxime obtained in one hour is 47 g., the molar yields being unchanged.
  • a process for the production of a product selected from the group of oximes and salts thereof by nitrosation of a hydrocarbon selected from the group of alkanes and cycloalkanes, containing at least carbon atoms in the molecule comprising the steps of:
  • a process for the production of a product selected from the group of oximes and salts thereof by nitrosation of a hydrocarbon selected from the group of alkanes and cycloalkanes containing at least 5 carbon atoms in their molecule comprising the steps of:
  • a process according to claim 2 wherein the average linear velocity of the reaction mixture through the reaction zone is of at least 3 cm. per second.
  • said strong mineral acid is an aqueous selected from the group consisting of 5090% by weight sulfuric acid, 5090% by weight phosphoric acid, and concentrated aqueous hydrochloric acid.
  • a process for the production of a product selected from the group of oximes and salts thereof by nitrosation of a hydrocarbon selected from the group of alkanes and cycloalkanes containing at least 5 carbon atoms in their molecule comprising the steps of:
  • a process for the production of a product selected from the group of oximes and salts thereof by nitrosation of a hydrocarbon selected from the group of alkanes and cycloalkanes containing at least 5 carbon atoms in their molecule comprising the steps of:
  • a process for manufacturing a product selected from the group consisting of cyclohexanone-oxime and salts thereof by nitrosation of cyclohexane comprising the steps of:
  • a process for the production of a product selected from the group of oximes and salts thereof by nitrosation of a hydrocarbon selected from the group of alkanes and cycloalkanes containing at least 5 carbon atoms in their molecule comprising the steps of:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US279323A 1962-05-23 1963-05-09 Process for nitrosation of hydrocarbons Expired - Lifetime US3320143A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR898554A FR1354780A (fr) 1962-05-23 1962-05-23 Procédé de nitrosation d'hydrocarbures

Publications (1)

Publication Number Publication Date
US3320143A true US3320143A (en) 1967-05-16

Family

ID=8779628

Family Applications (1)

Application Number Title Priority Date Filing Date
US279323A Expired - Lifetime US3320143A (en) 1962-05-23 1963-05-09 Process for nitrosation of hydrocarbons

Country Status (4)

Country Link
US (1) US3320143A (fr)
FR (1) FR1354780A (fr)
GB (1) GB1041056A (fr)
OA (1) OA01590A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140158522A1 (en) * 2012-06-26 2014-06-12 Toray Industries, Inc. Method of producing cycloalkanone oxime
US9932296B2 (en) 2012-06-27 2018-04-03 Toray Industries, Inc. Method of producing cycloalkanone oxime

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062812A (en) * 1959-04-23 1962-11-06 American Chemical Company Process for production of cyclic ketoximes and lactams from cycloalkanes by means of ionizing radiation
US3177133A (en) * 1961-11-17 1965-04-06 Basf Ag Separation of cycloalkanone oximes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062812A (en) * 1959-04-23 1962-11-06 American Chemical Company Process for production of cyclic ketoximes and lactams from cycloalkanes by means of ionizing radiation
US3177133A (en) * 1961-11-17 1965-04-06 Basf Ag Separation of cycloalkanone oximes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140158522A1 (en) * 2012-06-26 2014-06-12 Toray Industries, Inc. Method of producing cycloalkanone oxime
US9181177B2 (en) * 2012-06-26 2015-11-10 Toray Industries, Inc. Method of producing cycloalkanone oxime
US9932296B2 (en) 2012-06-27 2018-04-03 Toray Industries, Inc. Method of producing cycloalkanone oxime

Also Published As

Publication number Publication date
FR1354780A (fr) 1964-03-13
GB1041056A (en) 1966-09-01
OA01590A (fr) 1969-09-20

Similar Documents

Publication Publication Date Title
US2688592A (en) Photochemical process for preparing carbon tetrachloride
US3151051A (en) Synthesis of fluorine compounds
Henne Fluoroform
US3320143A (en) Process for nitrosation of hydrocarbons
Bordwell et al. Elimination Reactions in Cyclic Systems. I. cis Eliminations in the Cyclohexane and Cyclopentane Series1
US2948667A (en) Process for the photochemical chlorination of cyclohexane in the liquid phase
US3047482A (en) Production of oximes
JP4391013B2 (ja) 略無水媒体中のクロロホルム中でシクロドデカンを光ニトロソ化する方法
US3048634A (en) Production of ketoximes
US2202791A (en) Reaction of hydrocarbon compounds with gaseous chlorine and sulphur dioxide
US2818380A (en) Process for the manufacture of oximes
Duke et al. The Catalytic Decomposition of Bromate in Fused Alkali NITRATES1
US3062812A (en) Process for production of cyclic ketoximes and lactams from cycloalkanes by means of ionizing radiation
US3717561A (en) Photonitrosation of normal paraffins
US3405046A (en) Process for the manufacture of 2, 2, 3-trichlorobutane
US3775275A (en) Photonitrosation of normal paraffins
US1717951A (en) Method of producing nitrosyl halide
Fields et al. 366. Carbene chemistry. Part I. Reactions of fluoroalkyldiazo-compounds
US2514473A (en) Amides of fluorinated propionic
US2140507A (en) Production of ethyl chloride
US2697120A (en) Preparation of dichloracetaldehyde and chloral
US3312612A (en) Ketoxime production
US2324248A (en) Catalytic halo-substitution of saturated organic compounds
US3344187A (en) Process for preparing cycloalkanonoximes
GB949370A (en) Method of absorbing or dispersing and reacting gases in liquids