US3454617A - Process for the manufacture of borate esters of long chain aliphatic alcohols - Google Patents

Process for the manufacture of borate esters of long chain aliphatic alcohols Download PDF

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Publication number
US3454617A
US3454617A US628306A US3454617DA US3454617A US 3454617 A US3454617 A US 3454617A US 628306 A US628306 A US 628306A US 3454617D A US3454617D A US 3454617DA US 3454617 A US3454617 A US 3454617A
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Prior art keywords
reaction
boric acid
oxidation
temperature
oxygen
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Expired - Lifetime
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US628306A
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English (en)
Inventor
Manfred Fischer
Arnold Kotzschmar
Ulrich Schwenk
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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

  • the present invention relates to a porcess for the manufacture of long chain aliphatic alcohols by oxidation of unbranched paraffins in the presence of boric acid or of dehydration products thereof.
  • British Patent 353,047 expressely states that even in this temperature range the oxidation sets in noticeably no sooner than after one hour, thus that the boric acid must first be activated during this time.
  • the initially poor reaction rate is tolerated in favour of a decomposition, which takes place preferably at this temperature range, of the primarily formed hydroperoxide in direction towards alcohols, since at the same time at least the formation of undesired ketones and acids remains low.
  • a further lowering of the reaction temperature seems not to be possible in view of the obtainable reaction rate disclosed in French Patent 1,359,064, since in this patent, there is stated in Example 6, as comparison to Example 1, that at C. no reaction could be observed.
  • French Patent 1,166,679 attempts to by-pass this inconvenience by proposing as catalysts, instead of boric acid, phosphorous acid or arsenious acid, the esters of these acids which are better soluble in paraffin.
  • the use of these esters involves also the use of more complicated apparatus, because, in addition to the additional preparation of these esters, the lower alcohols liberated during the reaction by transesterification must also be recovered.
  • long-chain aliphatic alcohols can be prepared by the oxidation of paraffins containing from 10 to 25, preferably 12 to 15, carbon atoms, in the presence of boric acid and its dehydration products as catalysts and esterification components, and separation of unreacted paraflins and hydrolysis of the resulting borates, by adding to the paraffin preheated to at least C.
  • a gas mixture consisting of nitrogen and about 2 to about 10% by volume of oxygen, preferably about 4 to about 5% by volume of oxygen, is used in amounts of about 400 litres/hour/kg. of paraffin.
  • the process of the present invention permits homogeneous dissolution of the dehydrated boric acid in the paraffin.
  • the hitherto required removal by means of a stream of nitrogen of the water formed by the dehydration of ortho-boric acid is not necessary.
  • the boric acid is activated to such a degree that the oxidation sets in immediately upon introduction of the gas containing oxygen, which can be seen from the decrease of the oxygen content of the residual gas.
  • the activation of the dehydrated and dissolved boric acid is sufficient to permit carrying out the main reaction in a temperature range of from 150 to 155 C., after corresponding reduction of the reaction temperature, without the reaction rate being decreased or the reaction time being increased.
  • the activation of the dehydrated and dissolved ortho-boric acid is advantageously increased during a short induction period at the temperature at which the addition is carried out, by introducing oxygen-containing gases and then reducing the reaction tempearture to 150-155 C.
  • Another advantage of the process of the present invention is that the products obtained are practically colorless, whereas the oxidation products obtained at a higher reaction temperature show a distinct yellow color.
  • the secondary alcohols thus obtained serve for the preparation of surface-active compounds, especially as starting materials in the preparation of detergents, which are biologically easily decomposable.
  • EXAMPLE 1 200 g. of tridecane are filled into a glass frit tube having a ratio of length of diameter of 20:1 to :1, which is provided at its bottom with a filter plate through which oxygen diluted with nitrogen is introduced, and at its head with a cooler with water separator, and which is furthermore provided with an external, heatable jacket, and the tridecane is heated to a temperature in the range of 175- 180 C.
  • a stream of nitrogen may be passed through the reaction tube during heating.
  • 12 g. of ortho-boric acid (6% by weight, referred to the tridecane used) are added portionwise.
  • the ortho-boric acid dissolves homogeneously, under dehydration and simultaneous foaming, in the tridecane, If large single portions are added, it may be that a small residue of undissolved and only partially dehydrated boric acid accumulates on the filter plate, but this residue passes also in solution during the reaction.
  • reaction mixture is cooled to a temperature in the range of to C. and then treated at this temperature for 3 /2 hours with the same gas mixture and at the same introduction speed.
  • the vapors formed are continuously eliminated from the reaction vessel and condensed. After separation, the water is rejected, while the tridecane is recycled into the reaction zone.
  • the reaction rate with non-activated boric acid amounts to 9% only.
  • the reaction rate is higher, but the yield of alcohol is then about 50 to 60% only.
  • EXAMPLE 2 12 g. of ortho-boric acid are dehydrated as described in Example 1 at 175-l80 C., in 200 g. of pentadecane, and dissolved and then activated in the course of half an hour in the presence of oxygen. Oxidation is then continued at a temperature reduced to 130 C. After Working up of the reaction product, it has been found that about 12% of the parafiin used initially have been reacted, whereas it is stated in Example 6 of French Patent 1,359,064, that at 130 C., under the conditions described in said example, no reaction takes place.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US628306A 1966-04-06 1967-04-04 Process for the manufacture of borate esters of long chain aliphatic alcohols Expired - Lifetime US3454617A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF0048872 1966-04-06

Publications (1)

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US3454617A true US3454617A (en) 1969-07-08

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US (1) US3454617A (cg-RX-API-DMAC7.html)
JP (1) JPS506447B1 (cg-RX-API-DMAC7.html)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622647A (en) * 1969-09-11 1971-11-23 Texaco Inc Manufacture of alkene from alkane via boron esters
US5171875A (en) * 1991-01-11 1992-12-15 Lce Partnership Beta branched borate esters
US5856279A (en) * 1996-08-08 1999-01-05 The Lubrizol Corporation Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions
US10479748B2 (en) 2017-11-30 2019-11-19 Cambridge Enterprise Limited Oxidation of C1-9-alkanes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51126443U (cg-RX-API-DMAC7.html) * 1975-04-08 1976-10-13
JP6916365B1 (ja) * 2020-11-16 2021-08-11 株式会社日本触媒 第２級アルコールの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721181A (en) * 1952-10-09 1955-10-18 Kendall Refining Company Lubricant
US3243449A (en) * 1961-12-26 1966-03-29 Halcon International Inc Oxidation of hydrocarbons to borate esters
US3275695A (en) * 1962-12-19 1966-09-27 Halcon International Inc Recovery of boric acid for reuse in the oxidation of hydrocarbons
US3301887A (en) * 1959-12-18 1967-01-31 Exxon Research Engineering Co Production of cyclic unsaturated alcohols and borate esters
US3346614A (en) * 1965-01-27 1967-10-10 Continental Oil Co Preparation of alkyl metaborates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE552886C (de) * 1928-06-21 1934-04-19 Riebeck Sche Montanwerke Akt G Verfahren zur Gewinnung von Alkoholen in freier oder gebundener Form durch Oxydationvon festen oder fluessigen Kohlenwasserstoffen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721181A (en) * 1952-10-09 1955-10-18 Kendall Refining Company Lubricant
US3301887A (en) * 1959-12-18 1967-01-31 Exxon Research Engineering Co Production of cyclic unsaturated alcohols and borate esters
US3243449A (en) * 1961-12-26 1966-03-29 Halcon International Inc Oxidation of hydrocarbons to borate esters
US3275695A (en) * 1962-12-19 1966-09-27 Halcon International Inc Recovery of boric acid for reuse in the oxidation of hydrocarbons
US3346614A (en) * 1965-01-27 1967-10-10 Continental Oil Co Preparation of alkyl metaborates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622647A (en) * 1969-09-11 1971-11-23 Texaco Inc Manufacture of alkene from alkane via boron esters
US5171875A (en) * 1991-01-11 1992-12-15 Lce Partnership Beta branched borate esters
US5856279A (en) * 1996-08-08 1999-01-05 The Lubrizol Corporation Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions
US10479748B2 (en) 2017-11-30 2019-11-19 Cambridge Enterprise Limited Oxidation of C1-9-alkanes

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Publication number Publication date
JPS506447B1 (cg-RX-API-DMAC7.html) 1975-03-14

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