前苏联专利SU1720486A3 Method of synthesis of alcohols, ketones or their mixtures

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专利摘要:
Hydrocarbons, and particularly lower molecular weight alkanes and cycloalkanes, may readily be oxidized with air or O2 to form such products as alcohols, ketones, and the like selectively in high yields when there is employed as the catalyst a coordination complex containing an iron center and a halogenated ligand having the structure <CHEM> where Fe is iron; <CHEM> is a ligand; X is a halogen substituent of the ligand; and A is an anion.
公开号:SU1720486A3
申请号:SU884355942
申请日:1988-06-22
公开日:1992-03-15
发明作者:Э.Эллис Пол (Младший)；Э.Лаионз Джеймс；К.Майерз Херри (Младший)
申请人:Сан Рифайнинг Энд Маркетинг Ко. (Фирма)；
IPC主号:

专利说明:

are costly and unregenerable.
The disadvantage of this method is also the selectivity for the desired products.
The closest to the present invention is a method for producing alcohols, ketones or mixtures thereof by liquid-phase oxidation of saturated hydrocarbons or cyclohexane at elevated temperature and elevated pressure in an organic solvent medium. The catalyst used is metalloporphyrin complexes, such as Fe (DFT) C and Mn (DFT) C {where DFT means dianion (5,10,20-tetraphenylporphine). Iodosylbenzene, sodium hydrochloride, alkyl hydroperoxides, or other expensive non-regenerable oxidants are used as oxidizing agents. The disadvantage of this method is the low selectivity for the target product (up to 50%) and the use of non-regenerable oxidizers.
The purpose of the invention is to increase the selectivity of the process.
This goal is achieved in that according to the method of producing alcohols, ketones or their mixtures by oxidizing saturated Ci-C4 or cyclohexane hydrocarbons at elevated temperatures and elevated pressure in the presence of an iron halogen-containing catalyst in an organic solvent medium, the oxidation is carried out with oxygen or oxygen-containing gas. the catalyst uses the coordination complex of iron of the general formula:
(Fe-L-X) nA,
where the L-ligand is selected from the group including: porphyrins, phthalocyanines, isoin-valleys, nitrmodiphenolates; X is a substituent ligand of a and corresponds to a halogen; A is an anion selected from the group: halogen, acetate, azide, hydroxyl, if item 1 or A-nitrido or oxo, if item 2.
The method is illustrated by the following examples.
Examples 1-19. Propane in the amount of 1.36 mol was added to benzene in the amount of 42.2 g containing the catalyst. The solution is stirred for a set time at a set temperature under a pressure of 70.3 kg / cm 2 of air in an enameled autoclave. Products analyzed by GC.
The results of the process are given in Table. 1 (there are also comparative examples using other catalysts).
In tab. 1, the following notation is used: IPA is isopropyl alcohol, TPP is tetraphenyl porphyrin, TRGR is fluorinated tetraphenylporphyrin, Pc is phthalocyanine.
Examples 20-35. The process is conducted
as in example 1. Isobutane in the amount of 6-7 g is added to a solution of the catalyst in 25 ml of benzene and the solution is stirred at the set temperature for
0 set time. Products analyzed by GC.
The process conditions and results obtained are shown in Table. 2
Examples 36-39. In tab. 3 summarizes the oxidation of isobutane in the presence of ligands containing chlorine and / or bromine, and not fluorine, as in the examples table. 1 and 2. In each of the examples, 36-39.6 g of isobutane are stirred b at 80 ° C in 25 ml of benzene, in which
0 catalyst dissolved. During the whole experiment, an oxygen pressure of 7 atm is established, which is added as it is consumed. 3 used the following abbreviations: TCPR - tetra (2,6-dichlorophenyl)
5 porphyrinato, and TSRTVR-tetra (2,6-dichlorophenyl) tetrabromoporfininato.
Examples 40-41. The process is carried out similarly to the examples in Table. 3 with the exception that the hydrocarbon is pro-pan. 60 g of propane are dissolved in 48 ml of benzene catalyst solution and air is used at a pressure of 70 at.
The results of the process are given in Table. 4 (conventions are similar to those in Tables 1–4).
Examples 42-47. The process is carried out as in Examples 36-39.
Examples 42-47 show the use of various anionic components in the catalyst during the oxidation of isobutane.
The results of the process are given in Table. five.
Examples 48-51. The process is carried out in the same manner as in Examples 40-41. These examples of po5 refer to the use of various anionic components in the catalyst in the oxidation of propane.
The results of the process are given in Table. 6
0 Examples 52-53. Examples 52-53 show the use of perfluorophthalocyanine as a ligand in the oxidation of propane in acrylonitrile as a solvent (150 °, 3 hours).
5 The results of the process are given in Table-7.
EXAMPLE 54. Cyclohexane is oxidized by oxygen under a pressure of 7 at. In the presence of Fe (TPFP) N3 (0.017 mmol) at 90 ° C for 7.5 hours. The catalyst turnover is 408 and the predominant products are cyclohexanol and cyclohexanone. .
PRI me R 55. Isobutane oxide is OU at 80 ° C with oxygen using bispyridyl iminotetrafluoroisoindolinate (VRGP) as a catalyst. TBA selectivity is 92%.
Example 56. Example 55 is reproduced, but the catalyst is iron tetrafluoro-SAI EN-fluorinated Schiff base. TBA selectivity is 81%.
EXAMPLE 57 Methane is oxidized in the presence of Fe (EPc) N3 at 3 h under an air pressure of 35 at, a pressure of 106 106 atm, and 10 ml of a mixture of benzene-H20 as a solvent. The amount of methanol formed is 10.4 mmol / 100 g of the reaction solution.
Thus, this method allows to obtain the target product with a selectivity of up to 50% versus 22% in the prototype.

权利要求:
Claims (1)
[1]
Invention Formula
The method of producing alcohols, ketones or their mixtures by oxidizing saturated hydrocarbons Ci-C4 or cyclohexane at elevated temperature and pressure in the presence of an iron-halogen-containing catalyst in an organic solvent medium, characterized in that, in order to increase the selectivity of the process, the oxidation is carried out with oxygen or oxygen-containing gas, and as the catalyst used coordination complex of iron of the general formula
(Fe-L-X) nA,
where L is a ligand selected from the group including porphyrins, phthalocyanines, isoin-valleys, nitrilodiphenolates;
X is a ligand substituent and corresponds to halogen:
A - anion selected from the group: halogen, acetate, azide, hydroxyl, if l 1 or A - nitrido or oxo, if n 2,
Table 1
a) Comparative examples Mole (acetone + 1PA) per 1 mole of the used catalyst.
Mole (acetone + 1PA) on the I zero of the used catalyst in the reaction
Polar ratio of 1PA to acetone formed
a) “d“ H
Comparative examples
Mole of oxygen consumed per mole of catalyst
A mole of oxygen consumed per mole of catalyst in 1 centner.
The molar ratio of TBA (tert-butyl alcohol) ft to acetone formed during the reaction. Selectivity to TBA when TEPR catalysts are used always exceeds 90%.
36Fe (TCPP) Cl
37Fe (TCPTBP) Cl
38Fe (TCPP) N3
39Fe {TCPTBP) N9
Table 2
Ta lb and c and 3
1Yu Fe (TCPTBP) Cl 0.02331251251.0
41 Fe (TCPTBP) 0.0234.5 1252500.8
1720486
ten
Table

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同族专利:

公开号 | 公开日

NO170577C|1992-11-04|

DE3854316T2|1996-04-18|

EP0296712B1|1995-08-16|

EP0296712A2|1988-12-28|

JPH01125337A|1989-05-17|

JP2673307B2|1997-11-05|

MY103096A|1993-04-30|

EP0296712A3|1990-02-14|

US4900871A|1990-02-13|

CA1305974C|1992-08-04|

NO882169D0|1988-05-18|

DE3854316D1|1995-09-21|

NO882169L|1989-01-23|

NO170577B|1992-07-27|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

US07/066,666|US4900871A|1987-01-02|1987-06-26|Hydrocarbon oxidations catalyzed by iron coordination complexes containing a halogenated ligand|

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