Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/68—Preparation of metal alcoholates
  • C07C29/72—Preparation of metal alcoholates by oxidation of carbon-to-metal bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
  • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
  • C07C29/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only starting from compounds containing carbon-to-metal bonds and followed by conversion of the -O- metal to -OH groups

Definitions

• This invention relates to an improved method of-oxidizing aluminum trialkyls [to produce aluminum ftrialk'oxides, and more particularly the present invention is concerned with an economical method of effecting such an oxidation reaction.
• Alcohols may be produced from the hydrolysis of aluminum trialkoxides.
• the aluminum trialkyls from which the alkoxides are produced may be derived from the wellknown growth reaction between a low molecular aluminum trialkyl and an alpha-olefin, such as ethylene.
• An important step in the over-all process is the oxidation of the higher molecular weight aluminum trialkyls into the corresponding aluminum trialkoxides.
• side reactions occur resulting in the formation of such by-products as aldehydes, esters and hydrocarbons.
• the formation of by-products increases with temperature; consequently it is preferable to conduct the process .at the lowest temperature which is consistent with a reasonable reaction rate.
• Another object is to provide a substantially more economical method of oxidizing aluminum trialkyls to produce aluminum trialkoxides.
• the oxidation of aluminum trialkyl is preliminarily conducted with a view of effecting the highest yield of trialkoxide product consistent with minimum production of by-products.
• the first stage of oxidation is'done at a temperature above normal room temperature so that no expensive cooling equipment is required.
• the use of a temperature abovenormal room during the first stage appears to have no adverse effect in the over-all yield, when compared with an operation in whichthe entire reaction 'was conducted at a temperature below normal room;
• the aluminum-trialkyLwith orwithout'a solvent is contacted with the oxygen containing gas in an amount of'about 300 to 1,000 stan da-rd cubic feet per pound mole'aluminum in the aluminum trialkyl, abbreviated as rs. c.f. (measured at 0" .C- and 760 Hg),
• the temperature of reaction is usually between about 25 and C., more usually about 40 to 60 C.
• the reaction pressure can be varied widely, but generally it is about 15 to 50 p.s.i.g.
• the reaction time varies from about 1 to 50 hours, more usually about 3 to 7 hours.
• the first stage can comprise a series of oxidative steps or a single operation in which the yield of trialkoxide is obtained.
• the temperature is dropped to below normal room, and the reaction is completed to provide a yield greater than about 70- percent.
• the temperature of reaction is from about 10 to 15 C., more usually about 5 to 55C.
• the overall yield resulting from the second stage is usually about to 98 percent.
• the amount of oxygen containing gas employed relative to the reaction mass is about 50 to .160 sLc.f. per pound, more usually about to s.c.f. per pound.
• the re action is conducted at widely varying pressures, however, usually about 15 to 5 0 p.s.i.g.
• the second stage can be a single operation or a series of steps making up the same.
• the first and second stages of oxidation can be conducted as either batch or continuous operations.
• the oxygen containing gas and the feed material are charged, on a time basis, in the same relative proportions as specified hereinabove.
• the liquid reactant is contained in the oxidation vessel as a holdup 'so that the residence time may vary from about 1 to 5 0 hours, more usually about 3 to 7 hours.
• the aluminum trialkyl-employed as a starting materi has the following structural formula: r
• R R and R may be the same or different alkyl groups containing from about 4 to 30 carbon atoms or higher.
• these aluminum trialkyls are obtained through the reaction of a low molecular weight aluminum alkyl with a lower olefin, for example, ethylene, to form the so-called aluminum trialkyl growth product having the structural formula set forth above.
• the growth reaction is carried out, for example, by passing ethylene through aluminum triethyl, preferably in the presence of a diluent under a wide variety of reaction erably 90l20 C. and LOGO-3,500 p.s.i.g.
• C -C aluminum compounds such as tn'propylaluminum, tributylaluminum, triisobutylaluminum, diethylaluminum hydride, ethylaluminum dihydride, etc.
• C -C aluminum compounds such as tn'propylaluminum, tributylaluminum, triisobutylaluminum, diethylaluminum hydride, ethylaluminum dihydride, etc.
• ethylene other low molecular weight aliphatic moriml-dlfins, such as propylene and the like can be substituted.
• C -C olefins are preferred as the'growth hydrocarbon compound. 7
• the oxygen containing gas employed in :the oxidation reaction can beoxygen, a-iror any-other ga'scon'taining aluminumtriailkyl, with or-without a solvent.
• the solvent is essentially nonreactive and easily removed from the re-
• Various classes of compounds can be EXAMPLE 1
• the oxidation mixture consisted of 9 ml. of aluminum tn'hexyl and 15 ml. of n-decane.
• the reaction times were 12 hours at C. and five hours at 30, 45, 60 and 75 C.
• the air rate was 120 ml. per minute, and the pressure was 760 mm. of HgiS mm.
• 30 ml. of decane was added, and
• Table 11 Reaction temp., Alcohol, Run No. 0. percent yield
• Table 11 Reaction temp., Alcohol, Run No. 0. percent yield
• Run 1 in Table I is a single stage run at 0 C. and gave a yield of 94 percent; whereas Runs 1, 2 and 3 of Table II gave excellent yields in two stages. The two-stage operation compares very well with the run at 0 C.
• EXAMPLE 3 Aluminum trialkyl growth product was prepared by reacting aluminum triethyl with ethylene at a temperature of 120 C. and a pressure of 1,500 p.s.i.g. for about 2.5 hours. The product which had an "m value of 3.8 was oxidized in a series of runs with air or oxygen for time periods ranging from 5 to 12 hours in the presence of a solvent, the product being hydrolyzed and extracted to obtain the organic portion of the product. The percent yields of alcohol in each run were then ascertained, the results being presented in Table III:
• a process which comprises (1) first reacting aluminum alkyl growth product with an elemental oxygen containing gas at a temperature above normal room temperature not exceeding about 70 C. to effect a substantial conversion to the alkoxide but not more than about 70 percent and (2) thereafter reducing the temperature to below the reaction temperature of the first step, reacting the unreacted trialkyl growth product with elemental oxygen containing gas at said temperature below normal room temperature not below about 10 C. to efiect significantly more conversion to aluminum alkoxide than would result from continuing the reaction at the temperature of the first step for the same length of time.
• a process which comprises 1) first reacting aluminum trialkyls having alkyl groups containing about 4 to 30 carbon atoms per group with an elemental oxygen containing gas at a temperature above normal room temperature not exceeding about 70 C. to eifect a substan tial conversion to the alkoxide but not more than about 70 percent and (2) thereafter reducing the temperature to below the reaction temperature of the first step, reacting the unreacted aluminum trialkyl with elemental oxygen containing gas at said temperature below normal room temperature but not below about 10 C. to efiect significantly more conversion to aluminum alkoxide than would result from continuing the reaction at the temperature of the first step for the same length of time.
• a process which comprises. reacting aluminum trialkyl having about 4 to 30 carbon atoms per group with an elemental oxygen containing gas at a temperature of about 40 to 60 C. to effect a conversion to the alkoxide of about 45 to 65 percent and then contacting the resultant reaction product with elemental oxygen containing gas at a temperature of about -5 to 5 C. to eflect a total conversion to the alkoxide of about 80 to 98 percent.

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

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Cited By (6)

Citations (1)

• 1961
  • 1961-07-25 US US126498A patent/US3097226A/en not_active Expired - Lifetime
• 1963
  • 1963-07-08 FR FR940744A patent/FR1361808A/fr not_active Expired
• 1964
  • 1964-04-20 BE BE646780A patent/BE646780A/xx unknown

Patent Citations (1)

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