US3375265A - Production of trialkoxyboroxine - Google Patents

Production of trialkoxyboroxine Download PDF

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Publication number
US3375265A
US3375265A US485564A US48556465A US3375265A US 3375265 A US3375265 A US 3375265A US 485564 A US485564 A US 485564A US 48556465 A US48556465 A US 48556465A US 3375265 A US3375265 A US 3375265A
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United States
Prior art keywords
trialkoxyboroxine
tri
oxidation
boroxine
dodecane
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Expired - Lifetime
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US485564A
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English (en)
Inventor
Lloyd C Fetterly
George W Conklin
Kenneth F Koetitz
Friedrich G Helfferich
Peter W Gilderson
Stanley F Newman
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Shell USA Inc
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Shell Oil Co
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Priority to US485564A priority Critical patent/US3375265A/en
Priority to FR75281A priority patent/FR1491195A/fr
Priority to GB39530/66A priority patent/GB1122090A/en
Priority to BE686456D priority patent/BE686456A/xx
Priority to DE19661593424 priority patent/DE1593424A1/de
Priority to NL6612501A priority patent/NL6612501A/xx
Application granted granted Critical
Publication of US3375265A publication Critical patent/US3375265A/en
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    • 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
    • C07C29/52—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 in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed

Definitions

  • This invention relates to the production of alcohols by the controlled oxidation of paraflins. More particularly, this invention is concerned with the production of secondary alcohols by the controlled reaction of paraflins with an oxygen-containing gas in the presence of certain oxyboron compounds.
  • Oxidation of organic compounds with the aid of a variety of oxyboron compounds has been accomplished.
  • the oxidation of aliphatic hydrocarbons to secondary alkyl borate esters with oxygen in the presence of boric oxide or boric acid is known (see, for example, T. Hellthaler et al., German Patent 552,886, Apr. 19, 1934).
  • the borate esters can be hydrolyzed to yield corresponding secondary alcohols.
  • Saturated hydrocarbons can also be converted to alcohols by reaction with oxygen and borate esters or esters of boronic and borinic acids (see, for example, Netherlands application 649,l81, Feb. 22, 1965).
  • oxidation in the presence of metaboric acid is known (see, for example, S. N.
  • a principal object of the present invention to provide a rapid, efficient, and improved process for the controlled and continuous oxidation of parafiins.
  • a further object of the invention is to provide an improvide process for the production of predominantly secondary alcohols by carrying out the controlled oxidation of paraffins in the presence of certain boron compounds.
  • aliphatic secondary alcohols are prepared, preferentially over ketones, by contacting a paraflin in liquid phase at a temperature within the range of about 100 to about 300 C. with an oxygen-containing gas and carrying out the controlled oxidation of said parafiin in the presence of trialkoxyboroxine containing alkoxy of 4 or more carbon atoms to form from said parafiin secondary alcohols and their boron esters, followed by recovery of the secondary alcohols with means which provide for hydrolysis of the corresponding secondary alkyl borate ester.
  • the parafiins useful in the process of this invention are saturated aliphatic hydrocarbons of from 6 to 40 carbon atoms which can be normal or branched but preferably acyclic and essentially free of aromatics. Satisfactory results are obtained especially with parafiin designated RH Where R is an aliphatic hydrocarbyl of 8 to 30 carbons and preferably of 10 to carbons, especially alkyl of 10'to 20 carbons.
  • suitable hydrocarbons include n-hexane, n-octane, 2- ethylhexane, .n nonane, n dodecane, n tetradecane, eicosane, hexacosane, tr'iacontane, and the like, including their mixtures.
  • paraffin is oxidized in liquid phase with molecular oxygen, the controlled oxidation being carried out in the presence of trialkoxyboroxine and in the optional presence of a polyvalen't heavy metal catalyst.
  • the source of molecular oxygen is any oxygen-containing gas as, for example, air or oxygen diluted to any desired extent with an inert gas such as nitrogen, methane, carbon dioxide, and the like.
  • the trialkoxyboroxines useful in the process are those containing alkoxy of 4 or more carbon atoms. Especially preferred are those containing from 4 to 10 carbon atoms in each alkoxy, wherein the alkoxy contains at least 2 less carbons than the parafiin to be oxidized, with the proviso that the alkoxy contains at least 4 less carbons than the parafiin to be oxidized when the paraffin is of at least 10 carbon atoms. They maybe represented as oo-ia B-OQ or (QOBO) where Q is appropriate alkyl.
  • trialkoxyboroxines are particularly advantageous in that their selectivity to the production of desired secondary alcohol is high, accompanied by a low selectivity to production of ketone, as compared to the poorer selectivity to alcohol, accompanied by high selectivity to ketone, obtained with the aforementioned prior art oxyboron compounds.
  • continuous operation for example,
  • trialkoxyboroxines are that only one Q radical per boron atom is exposed to oxidative attack during the process as compared to three Q radicals per boron atom for the alkyl ortho borates. The net result is that oxidative losses of Q are much lower in the process of the invention.
  • Another advantage in the use of trialkoxyboroxines is their wide range of solubility in parafiin.
  • trialkoxyboroxines include tri(n-butoxyyboroxine, tri(isobutoxy)- boroxine, tri(sec butoxy)boroxine, tri(n heptoxy)- boroxine, tri(2 ethylhexoxy)boroxine, tri(n non0xy)- boroxine, tri(decoxy)boroxine, and the like.
  • the preparation of trialkoxyboroxines are Well summarized in H. Steinberg, Organoboron Chemistry, vol. 1, 445-454, Interscience Publisher s (Wiley), New York, 1964.
  • trialkoxyboroxine of alkoxy at least 2 to 4 less carbons than the paraffin to be oxidized as described herein-above, it is comparatively easy to conduct the oxidation under conditions of temperature and pressure at which the liberated lower alkanol (QOH) is rapidly stripped into the reactor off-gas. This rapid removal of the lower boiling alkanol assures that it will not remain in solution in the reactor and be subjected to degradation by oxidation.
  • the trialkoxyboroxine must have alkoxy of long enough carbon chain, i.e., at least 4, so that the trialkoxyboroxine is sufficiently high boiling to remain in the reaction system and not be stripped therefrom during reaction.
  • the alkoxy carbon content will preferably be as low as possible consistent with the aforesaid requirements so that there will be the fewest carbon atoms per boron atom exposed to oxidative attack, thereby lowering the oxidative losses of Q.
  • a suitable range may include, for example, the use of about 0.1 to about 1.5 mols of trialkoxyboroxine per mol of paraffin being oxidized.
  • a preferred range includes the use of about 0.2
  • a polyvalent heavy metal compound catalyst which is soluble in the reaction mixture may optionally be employed in a catalytically effective amount.
  • soluble salts of cobalt, manganese, lead, iron, and the like may be used in the form of acetate, octoate, stearate, and the like.
  • Preferred compounds include those such as cobalt octoate, cobalt stearate, and the like.
  • the amount of such additional reagent may be such that the reaction mixture contains from about 0.001 to 0.2% by weight (based on total weight of paratfin to be oxidized) of solu'bilized polyvalent heavy metal.
  • the controlled oxidation and concomitant esterification are conducted at a temperature Within the range of about 100 to about 300 C. at a pressure sufiicient to prevent excessive loss of paraffin with the exit gas. Pressures within the range of about 15 to about 1000 p.s.i.g. can be'employed. A preferred temperature range is from about 150 to about 190 C.
  • unconverted paraffin and ketone by-product are removed from the mixture by any suitable means, for example, by vacuum flashing.
  • the remaining product is a boron ester complex of the alkoxyboroxine and a secondary alcohol, from which the desired secondary alcohol is recovered by subsequent hydrolysis.
  • any suitable hydrolyzing agent well known to the art may be used, the preferred agent is water.
  • the hydrolysis is accomplished conveniently by adding water to the ester complex at a temperature sufiicient to maintain a liquid medium.
  • the complex is substantially hydrolyzed thereby to produce secondary alcohol, lower alkanol derived from the alkoxy of trialkoxyboroxine, and aqueous boric acid.
  • a preferred mode of operation encompasses separating the boric acid in aqueous phase and vacuum distilling the nonaqueous phase to obtain secondary alcohol free of lower alkanols, i.e. the light ends, and diol impurities arising in the oxidation, i.e. the heavy ends.
  • the secondary alcohol may be hydrogenated to reduce any carbonyl and unsaturation content.
  • the separated mixture of unconverted parafiin and ketone by-product may be hydrogenated to convert the ketone to paraffin or alcohol and the resulting material recycled to the oxidation reactor.
  • the ke- Itone may be removed by adsorption, for example, on alumina.
  • aqueous boric acid from the hydrolysis of the boron ester complex is reconverted to trialkoxyboroxine for reuse in the process.
  • Continuous operation can be achieved therein by a novel regeneration method.
  • hot aqueous boric acid from the hydrolysis is mixed with normally liquid, water-insoluble alkanol of at least 4 carbon atoms such that the alkanol to boron mole ratio is about 4 and the resulting mixture is fed to :a continuous esterification column which yields trialkyl ortho borate plus a slight excess of alkanol as bottoms and an alkanol-water azeotrope as overhead.
  • alkanol is returned to the column while water, saturated with alkanol, goes back to the hydrolyzer of the initial systempossibly after alkanol recovery.
  • 'Irialkyl ortho borate from the column is partially hydrolyzed to trialkoxyboroxine:
  • a preferred range of partial pressure of water vapor is from about 150 to about 200 mm. Hg. It is possible to use the oxidation react-or od-gas, if necessary admixed with steam, to carry out this partial hydrolysis step.
  • the partial hydrolysis to the alk-oxyboroxine may be carried out after addition of par-affin to the trialkyl ortho borate in continuous production.
  • the parafiin is preferably that which is to be oxidized, thereby providing a paraffin solution of the alkoxyboroxine which can be fed directly to the oxidation zone.
  • the partial hydrolysis is preferably carried to about 90% conversion rather than to completion because overshooting may result in formation of excessively viscous, gel-like, highly condensed polyborates, which are undesirable for the process of this invention.
  • Preferred trialkoxyboroxines to be used in such a continuous regeneration cycle are tri(n-butoxy) boroxine, tri(iso-butoxy)-b-oroxine, or tri(sec-butoxy) boroxine because of the relative volatilities of the various components of the system. Additionally, these butyl oxyboron compounds yield a more favorable alkanol/water azeot-r-ope, i.e. butanol/ water.
  • trialkoxyboroxine can be prepared in one step by feeding alkanol and boric acid in a ratio of from 1:1 to 12:1 to the esterification column and operating with alkanol reflux high enough to prevent crystallization of boric acid in the column.
  • Example I n-Dodeoane is contacted with 20% oleum at ambient temperature to remove aromatic components.
  • the n-dodecane is charged to a stainless-steel oxidation reactor vessel containing the trialkoxyboroxine indicated in Table 1 below.
  • a N /O mixture containing 10% by vol. of oxygen.
  • the mixture is heated to temperature indicated below for 4 hours.
  • the heat of reaction is removed by boiling water in internal coils. Unreacted n-dodecane and by-product ketone are removed from the resulting boron esters of secondary C alcohol by flashing at about 171 C., in two stages, one at 25 Hg and the other at 8 mm.
  • Example II In a manner similar to Example I, n-dodecane was oxidized in the presence of tributoxyboroxine and cobalt octoate. The results are summarized in Table 2.
  • Example III In a manner similar to Example I, n-dodecane was oxidized in a glass oxidation reactor vessel in the presence of tri(isobutyl) ortho borate and tri(isobutoxy)boroxine, respectively, to approximately the same dodecane conversion level.
  • the comparative results are summarized in Table 3.
  • Example IV n-Dodecane is passed through a continuous reaction cycle and oxidized in the presence of tri(n-butoxy) boroxine to yield dodecyl alcohols in the following manner:
  • n-Dodecane containing by weight of tri(n-butoxy) boroxine is pumped at a rate of 500 ml. per hour through a continuous oxidation reactor consisting of four wellstirred stages, each of 500 ml. of volume, arranged in series with respect to liquid flow and in parallel with respect to gas flow.
  • oxidizing gas nitrogen containing 10% by volume of oxygen, is sparged into each stage at a rate of 220 ml. per minute (STP).
  • STP ml. per minute
  • the reactor-temperature is maintained at 170 C. and the pressure, atmospheric.
  • 19.5% is oxidized, and 74.5% of the oxidation products b Tri(isobutoxy)boroxine.
  • dodecyl alcohols in the form of their borate esters.
  • the exit gas from the reactor is cooled to condense water and n-butanol, which are charged to the esterification column described below.
  • n-Butanol recovery by this condensation is 650 g. per 1000 g. of tri(n-butoxy) boroxine charged to the reactor.
  • the dodecyl alcohols are recovered as their crude borate esters after unreacted dodecane and by-product ketone have been overheaded in a continuous cyclone flasher. Ketone is removed from the dodecane by adsorption on alumina and the purified dodecane is returned to the reactor.
  • the flasher bottoms are hydrolyzed by a countercurrent stream of water under pressure at C., giving quantitative yield of crude free dodecyl alcohols together with some n-butanol and an aqueous solution of boric acid. Subsequent purification results in 730' g. of dodecyl alcohols per 1000 g. of dodecane reacted.
  • the aqueous boric acid solution, the condensate from the reactor exit gas, and sufficient n-butanol to supply a molar ratio of butanol to boric acid of 4:1 are fed to the 20th plate of a 25-plate Oldershaw (esterification) column.
  • thermosyphon reboiler at the base of the column has previously been charged with n-butanol and tri(n-butyl) ortho borate in a 1:1 ratio to furnish synthetic bottoms and is heated to about C.
  • Reaction on the plates of the column forms tri(n-butyl) ortho borate, which is then bled from the thermosyphon reboiler; water/butanol being azeotroped overhead, and the butanol returned as reflux after phase separation from the water.
  • the water from the phase separator, being saturated with n-butanol, is returned to the hydrolyzer.
  • a 95.1% yield of tri(nbutyl) ortho borate is obtained by this step.
  • Tri(n-butoxy)boroxine is produced from the above tri (n-butyl) ortho borate by controlled and partial hydrolysis with nitrogen, at atmospheric pressure, containing water vapor at 150 mm. Hg.
  • the tri(n-butyl) ortho borate is fed into a hydrolyzer, heated to C., and sparged with the wet nitrogen passed at the rate of ml. per min. per 100 g. of tri(n-butyl) ortho borate. This step results in 89% conversion to tri(n-butoxy)boroxine in about 5 hours, and a comparable amount of n-butanol is overheaded.
  • Thi butanol is used as feed for the above esterification column.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US485564A 1965-09-07 1965-09-07 Production of trialkoxyboroxine Expired - Lifetime US3375265A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US485564A US3375265A (en) 1965-09-07 1965-09-07 Production of trialkoxyboroxine
FR75281A FR1491195A (fr) 1965-09-07 1966-09-05 Préparation d'alcools
GB39530/66A GB1122090A (en) 1965-09-07 1966-09-05 Oxidation of paraffins to secondary aliphatic alcohols
BE686456D BE686456A (enrdf_load_stackoverflow) 1965-09-07 1966-09-05
DE19661593424 DE1593424A1 (de) 1965-09-07 1966-09-05 Verfahren zur Herstellung von Alkoholen
NL6612501A NL6612501A (enrdf_load_stackoverflow) 1965-09-07 1966-09-06

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BE (1) BE686456A (enrdf_load_stackoverflow)
DE (1) DE1593424A1 (enrdf_load_stackoverflow)
GB (1) GB1122090A (enrdf_load_stackoverflow)
NL (1) NL6612501A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3524893A (en) * 1967-12-22 1970-08-18 Texaco Inc Secondary alcohol manufacture
US3622647A (en) * 1969-09-11 1971-11-23 Texaco Inc Manufacture of alkene from alkane via boron esters
WO2006134074A3 (en) * 2005-06-13 2007-03-01 Basf Ag Process for synthesis of dialkoxyorganoboranes
US10479748B2 (en) 2017-11-30 2019-11-19 Cambridge Enterprise Limited Oxidation of C1-9-alkanes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2140252B1 (es) * 1995-01-11 2001-02-01 Repsol Quimica Sa Un procedimiento para la obtencion de fibras cortas y largas y sus telas de entrecruzamiento quimico por centrifugacion, estirado o extrusion de soles obtenidos mediante hidrolisis controlada de disoluciones de alcoxidos metalicos.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB939534A (en) * 1960-11-09 1963-10-16 Ici Ltd Improvements in and relating to the preparation of oxidation products of hydrocarbons
US3232704A (en) * 1962-03-21 1966-02-01 Exxon Research Engineering Co Process for recovering boric acid
GB1025443A (en) * 1962-01-15 1966-04-06 Stamicarbon Preparation of cyclic alcohols
GB1035624A (en) * 1961-12-07 1966-07-13 Ici Ltd Improvements in and relating to the preparation of alcohols

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB939534A (en) * 1960-11-09 1963-10-16 Ici Ltd Improvements in and relating to the preparation of oxidation products of hydrocarbons
GB1035624A (en) * 1961-12-07 1966-07-13 Ici Ltd Improvements in and relating to the preparation of alcohols
GB1025443A (en) * 1962-01-15 1966-04-06 Stamicarbon Preparation of cyclic alcohols
US3232704A (en) * 1962-03-21 1966-02-01 Exxon Research Engineering Co Process for recovering boric acid

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3524893A (en) * 1967-12-22 1970-08-18 Texaco Inc Secondary alcohol manufacture
US3622647A (en) * 1969-09-11 1971-11-23 Texaco Inc Manufacture of alkene from alkane via boron esters
WO2006134074A3 (en) * 2005-06-13 2007-03-01 Basf Ag Process for synthesis of dialkoxyorganoboranes
US20080200728A1 (en) * 2005-06-13 2008-08-21 Basf Aktiengesellschaft Process for Synthesis of Dialkoxyorganoboranes
US7858827B2 (en) 2005-06-13 2010-12-28 Basf Se Process for synthesis of dialkoxyorganoboranes
US20110060163A1 (en) * 2005-06-13 2011-03-10 Basf Se Process for Synthesis of Dialkoxyorganoboranes
US7973171B2 (en) 2005-06-13 2011-07-05 Elizabeth Burkhardt Process for synthesis of dialkoxyorganoboranes
US10479748B2 (en) 2017-11-30 2019-11-19 Cambridge Enterprise Limited Oxidation of C1-9-alkanes

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DE1593424A1 (de) 1970-07-30
NL6612501A (enrdf_load_stackoverflow) 1967-03-08
GB1122090A (en) 1968-07-31
BE686456A (enrdf_load_stackoverflow) 1967-03-06

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