Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
  • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
  • C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
  • C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings

Definitions

• the present invention relates to a process for the preparation of bicyclic ketones.
• the reaction is a chain reaction yielding, as first isolatable products, hydroperoxides of the formula ROOH, wherein R stands for ahydrocarbon radical, the subsequent selective decomposition of which gives the desired oxygenated compounds, either directly or by way of complex reactions.
• the primary objects of the present invention are:
• atomization device may advantageously be made of an atomization device of any suitable and per se conventional construction.
• reaction temperature between C. and 200 C., either by cooling or by supplying the necessary amount of heat over and above that already furnished by the reaction itself. Too low a temperature favors accumulation of hydroperoxides; too high a temperature reduces the yield because of the formation of secondary-products.
• the process according to the invention is characterized by the simultaneous employment, for the said hydrocarbons, of oxidation catalysts and of acid solvents which serve not only to decrease the induction period and to increase the speed of the selective reaction for the formation of the corresponding ketones, but also to reduce the content of hydroperoxides to a negligible value.
• the catalysts thus employed are cations of metals such as vanadium, chromium, manganese, copper, zinc, silver,
• tin, antimony, lead, bismuth, iron, nickel and cobalt are formed upon the dissolution of the metals or of an oxide or salt (for example chloride, nitrate, sulfate, etc.) of the said metals or of a soap (for example acetate, propionate, palmitate, stearate, naphthenate, etc.) of such metals, in the aforementioned acid solvent.
• concentration of catalysts relative to hydrocarbon can be reduced, according to this invention, down to very low values of the order of for example however, this figure is not at all intended to be lirnitative, since other concentrations may be employed.
• the acid solvents which can be employed according to the invention are straight-chain or branched-chain monobasic organic acids, particularly lower alk anoic acids, preferably acetic acid, propionic acid and butyric acid.
• the molar hydrocarbon solvent proportion of the hydrocarbon-solvent mixtures employed according to the invention be within the range V30 f0 20. employed.
• thermocouple may advantageously be employed for observing the temperature.
• Typical presently-preferred embodiments of the invention are set forth, by way of illustration, in the examples which follow. In such examples, the temperatures are set forth in degrees centigrade. Parts by weight" bear the same relation to parts by volume as do grams tov milliliters. Percentages are by weight.
• Example 1 A mixture of 583 parts by weight of tetralin (tetrahydronaphthalene), 315 parts by weight of acetic acid,
• CoCl- preliminarily dissolved in the acetic acid
• the oxidation apparatus which may conveniently be of Other molar proportions may, however, be
• the authenticity of the a-tetralone is confirmed inter alia by conversion thereof into the oxime and semi-carbazone and by its refractive index.
• oxygen-in this example as well as in those which follow. may also conveniently be supplied in the form of an oxygen-containing gas, such as air.
• Example 2 A mixture of 398 parts by weight of Tetralin, 176 parts by Weight of acetic acid, and 0.2 part by weight of manganous acetate (previously dissolved in the acetic acid) is introduced into the reaction vessel, and oxidation carried out after-the manner described in Example 1 for a period of 65 minutes at a temperature of 110.
• Example 3 A mixture of 398 parts by weight of Tetralin (3 mol.), 176 parts by weight of acetic acid and 0.2 part by weight of Ni(OH) (previously dissolved in the acetic acid) is introduced into-the reaction vessel and oxidation carried out after the manner described in Example 1 for a period of 75 minutes at a temperature of 125 C.
• the authenticity of the a-tetralone is confirmed inter alia by conversion thereof into the oxime and semicarbazone.
• Example 4 A mixture of 396 parts by weight of Tetralin, 222 parts by weight of propionic acid and 0.2 part by weight of CoCl (previously dissolved in the acetic acid) is intro dragonacted into the reaction vessel and oxidation carried out after the manner described in Example 1 for a period of 65 minutes at a temperature of 100 C.
• the resultant mixture contains less than 1% of peroxide.
• 297 parts by weight of unreacted Tetralin'and 388 parts by weight of tetralone (which represents a 76% molar yield relative to the reacted Tetralin) are recovered.
• Example 6 A mixture of 175 parts by weight of indane, 88 parts by weight of acetic acid and 0.2 partby weight of CoCl (previously dissolved in the acetic acid) is introduced into the reaction-vessel-and oxidation is carried out after the manner described in Example 1,-for a period of .65 minutes at a temperature of 85 C.
• the resultant mixture contains less than 1%. of peroxide, in addition to the unreacted indane and indanone After elimination of such acetic acid as may be present and distillation of the unreacted indane, indanone-1 is recovered.
• indanone-1 The authenticity of indanone-1 is confirmed inter alia by conversion thereof into 2-4-dinitrophenylhydrazone and by its refractive index. The yield of indanone relative to the reacted indane is 69% 1
• Example 7 There are recovered parts by weight of unreacted acenaphthene and 70 parts by weight of acenaphthenone. The authenticity of acenaphthenone is confirmed inter alia by conversion thereof into the oxime and the 2-4-dinitrophenylhydrazone.
• Example 8 A mixture of 336 parts by weight of diphenylmethane,
• T 118.5 parts by weight of acetic acid, and 0.2 part by weight of CoCl (preliminarily dissolved in the acetic acid) is introduced into the reaction vessel, and oxidation carried out as described in Example 1, except that a temperature'of is employed and the treating period is 'extended to 65 minutes.
• T heresultant mixture contains less than 0.8% of peroxide, in addition to unreacted diphenyl-' methane and benzophenone.
• the benzophenone is separated by precipitation thereof in the form of its oxime, and the unreacted diphenyl methane is distilled ofi.
• the particularly employed acid solvent may just as well be replaced byanother monobasic organic acid solvent.
• acetic acid it may be'replaced by propionic acid or butyric acid or the like, and vice versa.
• the particular oxidation catalyst therein employed may as well be replaced by equivalent quantities of other of the hereinbeforedescribed oxidation catalysts, such as for example the'cations of such metals as vanadium, chromium, manganese,- copper, zinc, silver, tin, antimony, lead, bismuth, iron,
• the acid solvent which is employed according to the present invention is not only a solvent for the oxidation catalyst but also for the hydrocarbon being oxidized.
• the oxidation catalysts are per se conventional, i. e. are known oxidation catalysts.
• the combination catalyst-solvent has a specific chemical effect since it secures the selectivity of the reaction and therefore the solvent is not to be considered only for its physical properties.
• a lower alkanoic acid solvent and of an oxidation catalyst said catalyst being formed by dissolving in the lower alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
• a lower alkanoic acid solvent and of an oxidation catalyst said catalyst being formed by dissolving in the lower alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
• oxidation catalyst in the presence of an oxidation catalyst and of an alkanoic acid solvent in a molar proportion of 1 to 20 relative to the hydrocarbon, said oxidation catalyst being formed by dissolving in the alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
• tetralone which comprises dissolving Tetralin and cobalt chloride in acetic acid and bubbling an oxygen-containing gas through said solution at a temperature of from about 80 to 200 C.
• indanone which comprises dissolving indane and cobalt chloride in acetic acid and bubbling an oxygen-containing gas' through said solution at a temperature of from about 80 to 200 C.
• acenaphthenone which comprises dissolving acenaphthene and cobalt chloride in butyric acid and bubbling an oxygen-containing gas through said solution at a temperature of from about 80 to 200 C.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1953
  • 1953-10-23 FR FR1095348D patent/FR1095348A/fr not_active Expired
• 1954
  • 1954-11-02 BE BE533179D patent/BE533179A/xx unknown
  • 1954-11-10 DE DEI9354A patent/DE1044059B/de active Pending
  • 1954-11-23 US US470797A patent/US2859247A/en not_active Expired - Lifetime
  • 1954-11-25 NL NL192671D patent/NL91100C/xx active
  • 1954-11-26 GB GB34387/54A patent/GB770478A/en not_active Expired

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