JPH05310601A - Oxidation of alkane - Google Patents

Abstract

PURPOSE:To obtain an alcohol or a ketone under mild condition at a low cost by oxidizing the corresponding alkane with oxygen in the presence of a transition metal catalyst and an aldehyde. CONSTITUTION:A 1-20C straight, branched or cyclic alkane is made to react with oxygen in the presence or absence of a proton source (preferably acetic acid or benzoic acid) and in the presence of a transition metal catalyst selected from chromium, manganese, iron, cobalt, nickel, copper, ruthenium and osmium- based catalysts, preferably iron-based catalyst or copper-based catalyst causing little environmental pollution and an aldehyde (preferably acetaldehyde, propionaldehyde, butanal or heptanal) to obtain an alcohol or ketone corresponding to the alkane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for oxidizing a linear, branched or cyclic alkane having 1 to 20 carbon atoms.
The alcohol or ketone obtained by the oxidation of the alkane is an important compound as a basic raw material when manufacturing various products such as resins such as nylon and polyester, medicines, agricultural chemicals, fragrances and dyes.

[0002]

2. Description of the Related Art As an effective use of alkanes which are abundant in nature, it has been desired to develop an efficient production method of alcohols and ketones by direct oxidation of alkanes. However, it is very difficult to oxidize an inactive alkane having no active functional group, and although there are many research examples, for example, the reaction conditions are strict (Chem. Process Eng.
ondon) 1969, 50 (6), 63.), which requires a complicated post-treatment step (J. Chem. Soc., Perkin Trans, I 1986, 94.
7.) etc. are not always enough.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing an alcohol or ketone advantageously by oxygen-oxidizing an alkane under mild conditions using a readily available catalyst. ..

[0004]

The present inventors have reached the present invention as a result of various studies in order to solve the above problems. That is, according to the present invention, a linear, branched or cyclic alkane having 1 to 20 carbon atoms is reacted with oxygen in the presence or absence of a proton source in the presence of a transition metal catalyst and aldehydes. A method for oxidizing an alkane, which comprises obtaining an alcohol or a ketone corresponding to the alkane.

In the present invention, examples of the linear, branched or cyclic alkane having 1 to 20 carbon atoms used as a raw material include methane, ethane, propane, n-butane, isobutane, n-pentane and n-hexane. , N-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-pentadecane, n-eicosane, 2-methylbutane,
2-methylheptane, 2-methyltetradecane, 2,6-dimethylheptane, 2,2,8-trimethylnonane, 3-methylpentane, 4-methylnonane, 4-n-propylnonane, 2,2-dimethylbutane, 2 , 2-Dimethylpentane, 3,3-Dimethylpentane, 2,2-Dimethylhexane, 3,3-Dimethylhexane, 3,
3-dimethylnonane, 2,2-dimethyltridecane, 3,3-dimethyltridecane, 4,4-dimethylheptane, 4,4-dimethyldecane, 5,5-dimethylnonane, 5,5-dimethyltridecane, 7,7-Dimethyltridecane, 2,2,8,8-Tetramethylnonane, 4,4,5,5-Tetramethyldecane, 5-Ethyl-5-n-propyldecane, Cyclopentane, Cyclohexane, Cycloheptane , Cyclooctane, cyclododecane, methylcyclopentane, methylcyclohexane, ethylcyclohexane, ethylcyclooctane, 1,2-dimethylcyclohexane, decalin, norbornane, adamantane and the like.

The alcohol or ketone which is the object compound of the present invention can be obtained as the corresponding alcohol or ketone by using the above alkane.
Examples of alcohols include methanol, ethanol, isopropyl alcohol, 2-butanol, tert-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol. , 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-
Nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-undecanol,
3-undecanol, 4-undecanol, 5-undecanol, 6-undecanol, 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 2-pentadecanol, 3-pentadecanol, 4- Pentadecanol, 5-pentadecanol, 6-pentadecanol, 7-pentadecanol, 8-pentadecanol, 2-eicosanol, 3-eicosanol, 4-eicosanol, 5-
Eicosanol, 6-Eicosanol, 7-Eicosanol, 8-Eicosanol, 9-Eicosanol, 10-Eicosanol, 2-Methyl-2-butanol, 3-Methyl-2-butanol, 2-Methyl-2-heptanol, 2-Methyl- 3-heptanol, 2-methyl-4-heptanol, 6-methyl-3-heptanol, 6-methyl-2-heptanol, 2-methyl-2-tetradecanol, 2-methyl-3-tetradecanol, 2- Methyl-4-tetradecanol, 2-methyl-5-tetradecanol, 2-methyl-6-tetradecanol, 2-methyl-7-tetradecanol, 13-methyl-7-tetradecanol, 13
-Methyl-6-tetradecanol, 13-Methyl-5-tetradecanol, 13-Methyl-4-tetradecanol, 13-Methyl-3-tetradecanol, 13-Methyl-2-tetradecanol, 2 , 6-Dimethyl-2-heptanol, 2,6-dimethyl
-3-heptanol, 2,6-dimethyl-4-heptanol, 2,
8,8-Trimethyl-2─nonanol, 2,8,8-Trimethyl-3─
Nonanol, 2,8,8-trimethyl-4-─Nonanol, 2,2,8-
Trimethyl-5-nonanol, 2,2,8-trimethyl-4-nonanol, 2,2,8-trimethyl-3-nonanol, 3-methyl-3
-Pentanol, 3-methyl-2-Pentanol, 4-methyl
-4-Nonanol, 4-Methyl-2-Nonanol, 4-Methyl-3
─ Nonanol, 4-methyl-5 ─ Nonanol, 6-methyl-4 ─
Nonanol, 6-Methyl-3-nonanol, 6-Methyl-2-nonanol, 4-n-propyl-4-nonanol, 4-n-propyl
-2-Nonanol, 4-n-propyl-3-nonanol, 4-n-propyl-5-nonanol, 6-n-propyl-4-nonanol,
6-n-Propyl-3-nonanol, 6-n-Propyl-2-nonanol, 3,3-Dimethyl-2-butanol, 2,2-Dimethyl-3
Pentanol, 4,4-Dimethyl-2-pentanol, 3,3-Dimethyl-2-pentanol, 2,2-Dimethyl-3-hexanol, 5,5-Dimethyl-3-hexanol, 5,5-Dimethyl -2─
Hexanol, 3,3-Dimethyl-2 hexanol, 4,4-Dimethyl-3 hexanol, 4,4-Dimethyl-2 hexanol, 3,3-Dimethyl-2-nonanol, 3,3-Dimethyl-4 ─ Nonanol, 3,3-dimethyl-5-nonanol, 7,7-dimethyl
-4-Nonanol, 7,7-Dimethyl-3-Nonanol, 7,7-Dimethyl-2-Nonanol, 2,2-Dimethyl-3-Tridecanol, 2,2-Dimethyl-4-Tridecanol, 2,2-Dimethyl -Five
─ Tridecanol, 2,2-dimethyl-6 ─ Tridecanol,
2,2-Dimethyl-7-tridecanol, 12,12-Dimethyl-6-
Tridecanol, 12,12-dimethyl-5-tridecanol,
12,12-Dimethyl-4 ─ tridecanol, 12,12-Dimethyl-3
─ Tridecanol, 12,12-Dimethyl-2 ─ Tridecanol, 3,3-Dimethyl-2 ─ Tridecanol, 3,3-Dimethyl-4
─ Tridecanol, 3,3-dimethyl-5 ─ Tridecanol,
3,3-Dimethyl-6-tridecanol, 3,3-Dimethyl-7-tridecanol, 11,11-Dimethyl-6-tridecanol, 1
1,11-Dimethyl-5-tridecanol, 11,11-Dimethyl-4
─ Tridecanol, 11,11-Dimethyl-3 ─ Tridecanol, 11,11-Dimethyl-2-─ Tridecanol, 4,4-Dimethyl
-2-heptanol, 4,4-dimethyl-3-heptanol, 4,4
-Dimethyl-2-decanol, 4,4-dimethyl-3-decanol, 4,4-dimethyl-5-decanol, 7,7-dimethyl-5-decanol, 7,7-dimethyl-4-decanol, 7,7 -Dimethyl
-3 decanol, 7,7-dimethyl-2-decanol, 5,5-dimethyl-2-nonanol, 5,5-dimethyl-3-nonanol,
5,5-Dimethyl-4-nonanol, 5,5-Dimethyl-2-tridecanol, 5,5-Dimethyl-3-tridecanol, 5,5-Dimethyl-4-tridecanol, 5,5-Dimethyl-6-tridecanol, 5,5-Dimethyl-7-tridecanol, 9,9-dimethyl
-6-Tridecanol, 9,9-dimethyl-5-Tridecanol, 9,9-dimethyl-4Tridecanol, 9,9-Dimethyl-3
─ Tridecanol, 9,9-dimethyl-2 ─ Tridecanol,
7,7-Dimethyl-2-tridecanol, 7,7-Dimethyl-3-tridecanol, 7,7-Dimethyl-4-tridecanol, 7,7-
Dimethyl-5-tridecanol, 7,7-Dimethyl-6-tridecanol, 2,2,8,8-Tetramethyl-3-nonanol, 2,2,
8,8-Tetramethyl-4-nonanol, 2,2,8,8-Tetramethyl-5-nonanol, 4,4,5,5-Tetramethyl-2-decanol, 4,4,5,5-Tetra Methyl-3-decanol, 6,6,7,7-tetramethyl-5-decanol, 6,6,7,7-tetramethyl-4─
Decanol, 6,6,7,7-tetramethyl-3-decanol, 6,
6,7,7-Tetramethyl-2-decanol, 5-ethyl-5-n-propyl-2-decanol, 5-ethyl-5-n-propyl-3-decanol, 5-ethyl-5-n-propyl -4-─ Decanol, 6-
Ethyl-6-n-propyl-5-decanol, 6-ethyl-6-n-
Propyl-4-decanol, 6-ethyl-6-n─propyl-3─
Decanol, 6-ethyl-6-n-propyl-2-decanol,
3-n-butyl-3-n-propyl-2-octanol, 4-butyl
-4-Ethyl-2-nonanol, 4-butyl-4-ethyl-3-nonanol, cyclopentanol, cyclohexanol,
Cycloheptanol, cyclooctanol, cyclododecanol, 1-methylcyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 1-methylcyclohexanol, 2-methylcyclohexanol,
3-methylcyclohexanol, 4-methylcyclohexanol, 1-ethylcyclohexanol, 2-ethylcyclohexanol, 3-ethylcyclohexanol, 4-ethylcyclohexanol, 1-cyclohexylethanol, 1-ethylcyclooctanol, 2-ethyl Cyclooctanol, 3-ethylcyclooctanol, 4-ethylcyclooctanol, 5-ethylcyclooctanol, 1-cyclooctylethanol, 1,2-dimethylcyclohexanol, 2,
3-dimethylcyclohexanol, 3,4-dimethylcyclohexanol, 9-decalol, 1-decalol, 2-decalol, endo-norborneol, exo-norborneol,
Examples thereof include 1-adamantanol and 2-adamantanol.

Examples of ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone,
3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-
Nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 6-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 6-dodecanone, 2-pentadecanone, 3-pentadecanone, 4-pentadecanone,
5-pentadecanone, 6-pentadecanone, 7-pentadecanone, 8-pentadecanone, 2-eicosanone, 3-eicosanone, 4-eicosanone, 5-eicosanone, 6-eicosanone, 7-eicosanone, 8-eicosanone, 9-eicosanone, 10- Eicosanone, 3-methyl-2-butanone, 2-methyl-3-heptanone, 2-methyl-4-heptanone, 6-methyl
-3-heptanone, 6-methyl-2 heptanone, 2-methyl-3
─ Tetradecanone, 2-Methyl-4-tetradecanone, 2-Methyl-5-tetradecanone, 2-Methyl-6-tetradecanone, 2-Methyl-7-tetradecanone, 13-Methyl-7-tetradecanone, 13-Methyl-6-tetradecanone , 13-Methyl-5-tetradecanone, 13-Methyl-4-tetratetracanone, 13-Methyl-3-tetradecanone, 13-Methyl-2-tetradecanone, 2,6-Dimethyl-3-heptanone, 2,6-Dimethyl-4 -Heptanone, 2,8,8-Trimethyl-3-nonanone,
2,8,8-Trimethyl-4-─nonanone, 2,2,8-trimethyl-5─
Nonanone, 2,2,8-trimethyl-4-nonanon, 2,2,8-trimethyl-3-nonanone, 3-methyl-2-pentanone, 4-methyl-2-nonanone, 4-methyl-3-nonanone, 4-methyl-5─
Nonanone, 6-Methyl-4-Nonanone, 6-Methyl-3-Nonanone, 6-Methyl-2-Nonanone, 4-n-Propyl-2-Nonanone, 4-n-Propyl-3-Nonanone, 4-n- Propyl-5─nonanone, 6-n-propyl-4─nonanone, 6-n-propyl-3─nonanone, 6-n-propyl-2─nonanone, 3,3-dimethyl-2─
Butanone, 2,2-dimethyl-3-pentanone, 4,4-dimethyl
-2-Pentanone, 3,3-Dimethyl-2-pentanone, 2,2-Dimethyl-3-hexanone, 5,5-Dimethyl-3-hexanone,
5,5-Dimethyl-2-hexanone, 3,3-Dimethyl-2-hexanone, 4,4-Dimethyl-3-hexanone, 4,4-Dimethyl-2
Hexanone, 3,3-Dimethyl-2-nonanone, 3,3-Dimethyl
-4-─nonanone, 3,3-dimethyl-5 ─nonanone, 7,7-dimethyl-4-nonanone, 7,7-dimethyl-3-nonanone, 7,7-dimethyl-2-nonanon, 2,2-dimethyl -3─Tridecanone, 2,
2-Dimethyl-4-tridecanone, 2,2-Dimethyl-5-tridecanone, 2,2-Dimethyl-6-tridecanone, 2,2-Dimethyl
-7-Tridecanone, 12,12-Dimethyl-6-Tridecanone, 1
2,12-Dimethyl-5-tridecanone, 12,12-Dimethyl-4
Tridecanone, 12,12-Dimethyl-3-Tridecanone, 12,1
2-Dimethyl-2-tridecanone, 3,3-Dimethyl-2-tridecanone, 3,3-Dimethyl-4-tridecanone, 3,3-Dimethyl
-5-Tridecanone, 3,3-Dimethyl-6-Tridecanone, 3,
3-Dimethyl-7-tridecanone, 11,11-Dimethyl-6-tridecanone, 11,11-Dimethyl-5-tridecanone, 11,11-Dimethyl-4-tridecanone, 11,11-Dimethyl-3-tridecanone, 11, 11-Dimethyl-2 ─ tridecanone, 4,4-dimethyl
-2-Heptanone, 4,4-Dimethyl-3-heptanone, 4,4-Dimethyl-2-decanone, 4,4-Dimethyl-3-decanone, 4,4-
Dimethyl-5-decanone, 7,7-Dimethyl-5-decanone, 7,
7-Dimethyl-4-decanone, 7,7-Dimethyl-3-decanone,
7,7-Dimethyl-2-decanone, 5,5-Dimethyl-2-nonanone, 5,5-Dimethyl-3-nonanone, 5,5-Dimethyl-4-nonanone, 5,5-Dimethyl-2-tridecanone, 5,5-dimethyl-3
─Tridecanone, 5,5-dimethyl-4 ─Tridecanone, 5,5-
Dimethyl-6-tridecanone, 5,5-Dimethyl-7-tridecanone, 9,9-Dimethyl-6-tridecanone, 9,9-Dimethyl-5
─Tridecanone, 9,9-dimethyl-4 ─Tridecanone, 9,9-
Dimethyl-3-Tridecanone, 9,9-Dimethyl-2-Tridecanone, 7,7-Dimethyl-2-Tridecanone, 7,7-Dimethyl-3
─Tridecanone, 7,7-Dimethyl-4─Tridecanone, 7,7-
Dimethyl-5-tridecanone, 7,7-Dimethyl-6-tridecanone, 2,2,8,8-Tetramethyl-3-nonanone, 2,2,8,8-Tetramethyl-4-nonanone, 2,2, 8,8-Tetramethyl-5-nonanone, 4,4,5,5-Tetramethyl-2-decanone, 4,4,5,5-
Tetramethyl-3-decanone, 6,6,7,7-tetramethyl-5-
Decanone, 6,6,7,7-tetramethyl-4-decanone, 6,6,7,
7-tetramethyl-3-decanone, 6,6,7,7-tetramethyl-2
-Decanone, 5-ethyl-5-n-propyl-2-decanone, 5-
Ethyl-5-n-propyl-3-decanone, 5-ethyl-5-n-propyl-4-decanone, 6-ethyl-6-n-propyl-5-decanone, 6-ethyl-6-n-propyl- 4-decanone, 6-ethyl
-6-n-propyl-3-decanone, 6-ethyl-6-n-propyl
-2-decanone, 3-n-butyl-3-n-propyl-2-octanone, 4-butyl-4-ethyl-2-nonanone, 4-butyl-4-ethyl-3-nonanone, cyclopentanone, cyclohexanone , Cycloheptanone, cyclooctanone, cyclododecanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-ethylcyclohexanone, 3-ethyl Cyclohexanone, 4-ethylcyclohexanone, cyclohexylmethylketone, 2-ethylcyclooctanone, 3-ethylcyclooctanone, 4-ethylcyclooctanone, 5-ethylcyclooctanone, cyclooctylmethylketone, 2,3-dimethylcyclohexanone , 3,4-dimethylcyclohexanone, 1-decalone, 2-
Decalon, norcamphor, 2-adamantanone, etc. may be mentioned.

As transition metal catalysts, chromium-based catalysts and
Ngan-based catalyst, iron-based catalyst, cobalt-based catalyst, nickel-based catalyst
Catalyst, Copper catalyst, Ruthenium catalyst, Osmium catalyst
Etc. Specifically, for example, Cr, CrCl₂・ NH₂
O, Cr₂(SO_Four)₃・ NH₂O, CrCl₃・ NH₂O, CrF₃
・ NH₂O, Cr (OAc)₃・ NH₂O, Cr (HCOO)₃・ NH₂O, Cr
(NO₃)₃・ NH₂O, CrNH_Four(SO_Four)₂・ NH₂O, CrPO
_Four・ NH₂O, Cr₂O₃・ NH₂O, CrO₃, Cr (acac)₃, M
n, MnCl₂・ NH₂O, MnBr₂nH₂O, MnF₂, MnSO_FournH₂O,
 Mn (NO₃)₂・ NH₂O, Mn (OAc)₂・ NH₂O, Mn (ClO_Four)
₂・ NH₂O, MnHPO _Four・ NH₂O, MnCO₃・ NH₂O, Mn (OAc)
₃・ NH₂O, MnO₂, Mn (acac)₂・ NH₂O, Mn (acac)₃・
nH₂O, Fe, Fe (CO)_Five, Fe (CO)₉, Fe (CO)₁₂, FeCl₂・
nH₂O, FeBr₂・ NH₂O, FeSO_Four・ NH₂O, Fe (ClO_Four)
₂・ NH₂O, FeSO_Four(NH_Four)₂SO_Four・ NH₂O, Fe₃(PO
_Four)₂・ NH₂O, FeCl₃・ NH₂O, FeF₃・ NH₂O, Fe₂
(SO _Four)₃・ NH₂O, Fe (NO₃)₃・ NH₂O, Fe (OAc)₃, F
e (ClO_Four)₃・ NH₂O, FeNH _Four(SO_Four)₂・ NH₂O, FePO
_Four・ NH₂O, Fe₂O₃, Fe₃O_Four, Fe (acac)₃, Co, Co
Cl₂・ NH₂O, CoBr₂・ NH₂O, CoI₂・ NH₂O, CoF₂・
nH₂O, CoSO_Four・ NH ₂O, Co (NO₃)₂・ NH₂O, Co (OAc)
₂・ NH₂O, CoSO_Four(NH_Four)₂SO_Four・ NH₂O, Co₃(PO_Four)₂
・ NH₂O, CoCO₃, Co (OH)₂, Co (acac)₂・ NH₂O, Co (acac)
₃・ NH₂O, Co₃O_Four, Ni, NiCl₂・ NH₂O, NiBr₂・ NH₂O, Ni
I₂・ NH₂O, NiF₂・ NH₂O, NiSO_Four・ NH₂O, Ni (NO₃)₂・ NH
₂O, Ni (OAc)₂・ NH₂O, Ni (HCOO)₂・ NH₂O, Ni (ClO_Four)₂・
nH₂O, NiSO_Four(NH_Four)₂SO_Four・ NH₂O, NiCO₃, Ni (OH)₂, Ni (a
cac)₂・ NH₂O, NiO, Ni₂O₃, Cu, CuCl, CuBr, CuI, CuC
l₂・ NH₂O, CuBr₂, CuF₂, CuSO_Four・ NH₂O, Cu (NO₃)₂・ NH
₂O, Cu (OAc)₂・ NH₂O, Cu (ClO_Four)₂・ NH₂O, Cu (OH)₂, Cu
(OCH₃)₂, Cu₃(PO_Four)₂・ NH₂O, CuO, Cu₂O, Cu (acac)₂, R
u, Ru₃(CO)₁₂, RuCl₂(PPh₃)₃, RuCl₃・ NH₂O, RuO₂・ NH₂
O, RuO_Four, Os, OsCl₃・ NH₂O or OsO_Four(Where n
Usually represents an integer of 0-12. ) Etc.
More specifically, iron-based catalysts and copper-based catalysts, which have less environmental pollution, are listed.
Be done.

Further, these catalysts may be mixed and used,
You may use what carried these catalysts on heteropoly acid, silica gel, carbon powder, a polymer, etc. The amount used is not particularly limited, but is usually in the range of 0.01 to 200 mol% with respect to the alkane, and preferably 0.
It is in the range of 1-5 mol%.

The aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal, decanal, 2-methylpropanal, cyclohexanecarboxaldehyde, isovaleraldehyde, pivalaldehyde, benzaldehyde, p-chloro. Benzaldehyde,
Examples thereof include m-chlorobenzaldehyde, p-tolualdehyde, p-anisaldehyde, paraformaldehyde, paraaldehyde, etc. Among them, acetaldehyde, propionaldehyde, butanal and heptanal, which are easily available and have a low molecular weight, are preferable. The amount used is not particularly limited, but is usually
The range is 0.1-1000 mol%, preferably 1 mol%
-In the range of 400 mol%. The addition of the proton source is particularly effective when the transition metal catalyst is a simple substance or a heterogeneous catalyst.

As the proton source, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, trifluoroacetic acid, propanoic acid, butyric acid, heptanoic acid, decanoic acid, benzoic acid, p-toluenesulfonic acid,
Examples thereof include hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid, water and the like, preferably acetic acid and benzoic acid. The amount used is not particularly limited, but is usually 1-100 with respect to the transition metal catalyst.
It is in the equivalent range. However, when the transition metal catalyst contains water, a proton source is not particularly required. In the present invention, a solvent may be used, and examples of the solvent to be used include halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, esters such as ethyl acetate, nitriles such as acetonitrile, benzene, toluene, xylene, Examples thereof include aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene.

As oxygen used in the present invention, air may be used in addition to oxygen, and the supply method thereof is not particularly limited, but may be blowing, atmosphere, etc., and may be atmospheric pressure or pressurized. The reaction temperature is usually in the range of 0 ° C to the reflux temperature of the reaction mixture, preferably 20 ° C to
It is in the range of 80 ° C.

The reaction time is not particularly limited, but the reaction mixture may be analyzed by GC or the like and the reaction end point may be the time when the production rate of the desired alcohol or ketone reaches a peak, usually 1 hour-1 week. It is a range. In this reaction, the aldehydes used become the corresponding carboxylic acids and can be easily separated from the desired product.

After completion of the reaction, for example, the reaction mixture is washed with an aqueous solution of sodium sulfite and an aqueous solution of sodium hydrogencarbonate, concentrated, and if necessary, rectified to give the desired alcohol or ketone.

[0015]

INDUSTRIAL APPLICABILITY The present invention makes it possible to obtain an alcohol or a ketone from an alkane in one step with oxygen in the presence or absence of a proton source under mild conditions using an easily available transition metal catalyst and aldehydes. It is an industrially excellent manufacturing method.

[0016]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Examples 1 to 26 A mixture of 272 mg of adamantane, 3 mol% of catalyst (vs. adamantane), 4 mg of acetic acid and 10 ml of dichloromethane was dissolved in 2 ml of dichloromethane at 25 ° C. under an oxygen atmosphere at 25 ° C. The mixture was added dropwise over a period of time and stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the results shown in Table 1 were obtained. The product was quantified by the GC-IS method and the structure was identified by the GC-MS.

[0018]

[Table 1]

[0019]

[Table 2] ^{* 1} vs. adamantane, ^{* 2} vs. adamantane, figures in parentheses are against adamantane consumed

Examples 27 to 36 A mixture of 272 mg of adamantane, 3 mol% of catalyst (vs. adamantane), 264 mg of acetaldehyde and 12 ml of dichloromethane was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. The reaction mixture was analyzed by GC and the results shown in Table 2 were obtained.

[0021]

[Table 3] ^{* 1} vs. adamantane, ^{* 2} vs. adamantane, figures in parentheses are against adamantane

Examples 37 to 40 In a mixture of 272 mg of adamantane, 3.4 mg of Fe and 10 ml of dichloromethane, 4 equivalents of aldehyde (vs. adamantane) were added to 2 m of dichloromethane at 25 ° C. under an oxygen atmosphere.
The solution dissolved in 1 was added dropwise over 2 hours, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and
The results shown in are obtained.

[0023]

[Table 4] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 41 to 44 16 parts of RuCl ₃ .3H ₂ O were used instead of 3.4 mg of Fe.
The same operation as in Example 37 was carried out except that mg was used.
The results shown in 4 were obtained.

[0025]

[Table 5] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 45 to 49 Adamantane 272 mg, Cu (OH) ₂ 5.9 mg,
A mixture of 3 equivalents of aldehyde (vs. adamantane) and 12 ml of dichloromethane was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. The reaction mixture was analyzed by GC and the results shown in Table 5 were obtained.

[0027]

[Table 6] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 50-52 Adamantane 272 mg, RuCl ₃ .3H ₂ O 16
mg, acetic acid 4 mg and solvent 10 ml in a mixture of heptanal 914 mg and solvent 2 ml at 25 ° C. under oxygen atmosphere
The solution dissolved in was added dropwise over 2 hours, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the table
The results shown in 6 were obtained.

[0029]

[Table 7] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 53 to 56 Adamantane 272 mg, Fe 3.4 mg, acetic acid 4 mg
A solution of heptanal in 2 ml of a dichloromethane solvent was added dropwise to a mixture of 10 ml of dichloromethane and 10 ml of dichloromethane at 25 ° C under an oxygen atmosphere over 2 hours, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and shown in Table-7.
The results shown in are obtained.

[0031]

[Table 8] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 57 to 59 In place of 3.4 mg of Fe, 16 of RuCl ₃ .3H ₂ O was used.
The same operation as in Example 53 was carried out except that mg was used.
The results shown in 8 were obtained.

[0033]

[Table 9] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 60 to 61 To a mixture of 272 mg of adamantane, 10 ml of Fe, acetic acid and dichloromethane at 25 ° C. under an oxygen atmosphere, a solution of 914 mg of heptanal in 2 ml of dichloromethane was added dropwise over 2 hours, and at the same temperature, a further 15 parts were added. Stir for hours. The reaction mixture was analyzed by GC and the results shown in Table 9 were obtained.

[0035]

[Table 10] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 62 to 63 The same operation as in Example 60 was carried out except that RuCl ₃ .3H ₂ O was used instead of Fe and heptanal was 685 mg, and the results shown in Table 10 were obtained.

[0037]

[Table 11] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 64-65 A mixture of 272 mg of adamantane, 1.1 mg of Fe, acetic acid and 10 ml of dichloromethane was added at 25 ° C. under an oxygen atmosphere.
Then, a solution prepared by dissolving 914 mg of heptanal in 2 ml of dichloromethane was added dropwise over 2 hours, and the mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC, Table 1
The results shown in 1 were obtained.

[0039]

[Table 12] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 66 to 68 In place of 1.1 mg of Fe, 16 parts of RuCl ₃ .3H ₂ O were added.
Using the same procedure as in Example 64, except that the amount of heptanal was 685 mg, the results shown in Table 12 were obtained.

[0041]

[Table 13] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 69 to 71 Adamantane 272 mg, Fe 1.1 mg, acid 1 mol%
(To adamantane) and dichloromethane (10 ml) in an oxygen atmosphere at 25 ° C., heptanal (914 mg)
Was added dropwise to 2 ml of dichloromethane over 2 hours, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the results shown in Table 13 were obtained.

[0043]

[Table 14] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 72 to 75 Adamantane 272 mg, Cu (OH) ₂ 5.9 mg,
A mixture of 264 mg of acetaldehyde, 3 mol% of acid (vs. adamantane) and 12 ml of dichloromethane was stirred at 25 ° C for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 14 were obtained.

[0045]

[Table 15] ^{* 1} vs. Adamantane ^{* 2} vs. Adamantane, Figures in parentheses are against consumption Adamantane

Examples 76 to 81 Alkane 2 mmol, Fe 1.1 mg, acetic acid 1.2 mg
And 10 ml of dichloromethane in an oxygen atmosphere at 25 ° C., 914 mg of heptanale in dichloromethane 2
The solution dissolved in ml was added dropwise over 2 hours, and the mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC,
The results shown in Table-15 were obtained. For the product, GC-
Quantification by IS method and structure identification by GC-MS were performed.

[0047]

[Table 16] ^{* 1} to alkane, ^{* 2} to alkane, figures in parentheses are to consumed alkane, ^{* 3} 2-ol: 3-ol: 4-ol = 46: 36:
18 ^{* 4} 2-on: 3-on: 4-on = 44:39:17 ^{* 5} 2-ol: 3-ol: (4 + 5) all = 28: 2
2: 50 ^{* 6} 2-on: 3-on: (4 + 5) -on = 24:
24:52 ^{* 7} 1-ol: 2-ol: 3-ol: 4-ol =
69: 6: 18: 7 ^{* 8} 2-on: 3-on: 4-on = 20: 57: 23

Examples 82 to 86 In place of 1.1 mg of Fe, 1% of RuCl ₃ .3H ₂ O was added.
6 mg was used, heptanal was 685 mg, and the same operation as in Example 76 was performed except that the alkane was changed, and the results shown in Table 16 were obtained.

[0049]

[Table 17] ^{* 1} vs. alkane, ^{* 2} vs. alkane, figures in parentheses are vs. consumed alkane, ^{* 3} 2-on: 3-on: 4-on = 47: 33: 20 ^{* 4} 2-ol: 3-ol :( 4 + 5) All = 35: 2
4:41 ^{* 5} 2-on: 3-on: (4 + 5) -on = 21: 26: 5
3 ^{* 6} 1-ol: 2-ol: 3-ol: 4-ol =
87: 3: 7: 3 ^{* 7} 2-on: 3-on: 4-on = 13: 62: 25

Examples 87-91 A mixture of 13.3 mmol of alkane, 0.6 mg of Fe, 0.6 mg of acetic acid and 10 ml of dichloromethane was added to a solution of 152 mg of heptanal in 2 ml of dichloromethane at 25 ° C. under an oxygen atmosphere for 2 hours. Was added dropwise, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture is G
Analysis by C gave the results shown in Table-17.

[0051]

[Table 18] ^{* 1} vs. heptanal, ^{* 2} vs. heptanal, figures in parentheses are against consumed alkane, ^{* 3} 2-ol: 3-ol: 4-ol = 41: 35:
24 ^{* 4} 2-on: 3-on: 4-on = 44:38:18 ^{* 5} 2-ol: 3-ol: (4 + 5) all = 30: 2
2: 48 ^{* 6} 2-on: 3-on: (4 + 5) -on = 24:
21:55 ^{* 7} 1-ol: 2-ol: 3-ol: 4-ol =
86: 4: 8: 2 ^{* 8} 2-on: 3-on: 4-on = 17:63:20

Example 92 The same operation as in Example 91 was carried out except that 2.6 mg of RuCl ₃ .3H ₂ O was used instead of 0.6 mg of Fe, and the following results were obtained. -Conversion rate: 70% (relative to heptanal) Methylcyclohexanol yield: 61% (relative to heptanal), 88% (relative to consumed methylcyclohexane), 1-ol: 2-ol: 3-ol: 4-ol =
91: 2: 5: 2 Methylcyclohexanone Yield: 12% (vs. heptanal), 8% (vs. methylcyclohexane consumed), 2-one: 3-one: 4-one = 23: 58: 19

Examples 93 to 97 13.3 mmol of alkane, RuCl ₃ .3H ₂ O
2.6 mg, acetic acid 0.6 mg and ethyl acetate 10 ml
Heptanal 152 in an oxygen atmosphere at 50 ° C.
A solution of mg in ethyl acetate (2 ml) was added, and the mixture was stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the table
The result shown in 18 was obtained.

[0054]

[Table 19] ^{* 1} vs. heptanal, ^{* 2} vs. heptanal, figures in parentheses are for consumption alkanes ^{* 3} 2-ol: 3-ol: 4-ol = 40: 40:
20 ^{* 4} 2-on: 3-on: 4-on = 41: 41: 18 ^{* 5} 2-ol: 3-ol: (4 + 5) all = 30: 2
4:46 ^{* 6} 2-on: 3-on: (4 + 5) -on = 22:
36:42 ^{* 7} 1-ol: 2-ol: 3-ol: 4-ol =
96: 1: 2: 1 ^{* 8} 2-on: 3-on: 4-on = 17: 62: 21

Examples 98 to 103 Alkane 2 mmol, Fe 1.1 mg, acetic acid 1.2 mg
A solution of 352 mg of acetaldehyde in 2 ml of dichloromethane was added dropwise to a mixture of 10 ml of dichloromethane and 10 ml of oxygen at 25 ° C. over 2 hours, and the mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the results shown in Table 19 were obtained.

[0056]

[Table 20] ^{* 1} to alkane, ^{* 2} to alkane, figures in parentheses are to consumed alkane, ^{* 3} 2-ol: 3-ol: 4-ol = 40: 40:
20 ^{* 4} 2-on: 3-on: 4-on = 37: 42: 21 ^{* 5} 2-ol: 3-ol: (4 + 5) all = 27: 2
7:46 ^{* 6} 2-on: 3-on: (4 + 5) -on = 22: 33: 4
4 ^{* 7} 1-ol: 2-ol: 3-ol: 4-ol =
64: 7: 22: 7 ^{* 8} 2-on: 3-on: 4-on = 28:52:20 ^{* 9} 1-ol: 2-ol = 92: 8

Examples 104-109 A mixture of 2 mmol of alkane, 5.9 mg of Cu (OH) _2, 1.2 mg of acetic acid, 264 mg of acetaldehyde and 12 ml of dichloromethane at 25 ° C. under an oxygen atmosphere at 17 ° C.
Stir for hours. The reaction mixture was analyzed by GC and the results shown in Table 20 were obtained.

[0058]

[Table 21] ^{* 1} to alkane, ^{* 2} to alkane, figures in parentheses are to consumed alkane, ^{* 3} 2-ol: 3-ol: 4-ol = 40: 34:
26 ^{* 4} 2-on: 3-on: 4-on = 40:43:17 ^{* 5} 2-ol: 3-ol: (4 + 5) all = 20: 2
0:60 ^{* 6} 2-on: 3-on: (4 + 5) -on = 27: 27: 4
6 ^{* 7} 1-ol: 2-ol: 3-ol: 4-ol =
66: 8: 21: 5 ^{* 8} 2-on: 3-on: 4-on = 18:61:21

Example 110 Cyclohexane 20.2 g, Fe 3.4 mg, acetic acid 3.
A mixture of 6 mg and 1.055 g of paraaldehyde was stirred at 70 ° C. under an oxygen atmosphere for 1 week. GC the reaction mixture
The following results were obtained. Cyclohexanol yield: 5.8% (vs. paraaldehyde) turnover number: 23 Cyclohexanone yield: 29.3% (vs. paraaldehyde) turnover number: 102

Example 111 The same operation as in Example 110 was carried out except that 2.741 g of heptanal was used instead of paraaldehyde and the amount of acetic acid was 360 mg, and the following results were obtained. Cyclohexanol yield: 9.6% (vs. heptanal) Turnover number: 38 Cyclohexanone yield: 22.5% (vs. heptanal) Turnover number: 90

Example 112 Acetaldehyde 1.057 instead of paraaldehyde
Example 110 except that g is used and acetic acid is 360 mg.
The same operation was performed and the following results were obtained. Cyclohexanol yield: 3.4% (vs acetaldehyde) Turnover number: 14 Cyclohexanone yield: 8.7% (vs acetaldehyde) Turnover number: 35

Example 113 67.3 g of cyclohexane, 11 mg of Fe, 12 m of acetic acid
g and acetaldehyde (3.52 g) were placed in an autoclave and pressurized to oxygen (8 kg / cm ² ) at 70 ° C.
It was stirred for 24 hours. The reaction mixture was analyzed by GC with the following results. Cyclohexane conversion: 23.1% (to acetaldehyde) Cyclohexanol yield: 9.1% (to acetaldehyde) 39.5% (to cyclohexane consumption) Turnover number: 36 Cyclohexanone yield: 27.4% (to acetaldehyde) ) 59.5% (vs. cyclohexane consumed) Turnover number: 110

Example 114 Cyclohexane 6.73 g, Fe 1.1 mg, acetic acid 1.
A mixture of 2 mg and 352 mg of acetaldehyde was placed in an autoclave and stirred at 70 ° C. for 5 days under air pressure (10 kg / cm ² ). The reaction mixture was analyzed by GC,
The following results were obtained. Cyclohexane conversion rate: 20.1% (to acetaldehyde) Cyclohexanol yield: 7.7% (to acetaldehyde) 38.3% (to cyclohexane consumption) Turnover number: 31 Cyclohexanone yield: 24.8% (to acetaldehyde) ) 61.7% (vs. cyclohexane consumed) Turnover number: 99

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 19, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

As transition metal catalysts, chromium-based catalysts and
Ngan-based catalyst, iron-based catalyst, cobalt-based catalyst, nickel-based catalyst
Catalyst, Copper catalyst, Ruthenium catalyst, Osmium catalyst
Etc. Specifically, for example, Cr, CrCl₂
・ NH₂O, Cr₂(SO_Four)₃・ NH₂O, CrCl
₃・ NH₂O, CrF₃・ NH₂O, Cr (OAc) ₃
・ NH₂O, Cr (HCOO)₃・ NH₂O, Cr (N
O₃)₃・ NH₂O, CrNH_Four(SO_Four)₂・ NH₂
O, CrPO_Four・ NH₂O, Cr₂O₃・ NH ₂O, C
rO₃, Cr (acac)₃, Mn, MnCl₂・ NH
₂O, MnBr ₂・ NH₂O, MnF₂, MnSO_Four・
nH₂O, Mn (NO₃)₂・ NH₂O, Mn (OA
c)₂・ NH₂O, Mn (ClO_Four)₂・ NH₂O, M
nHPO_Four・ NH₂O, MnCO₃・ NH₂O, Mn
(OAc)₃・ NH₂O, MnO₂, Mn (acac)
₂・ NH₂O, Mn (acac)₃・ NH₂O, Fe,
Fe (CO)_Five, Fe (CO)₉, Fe (CO)₁₂, F
eCl₂・ NH₂O, FeBr ₂・ NH₂O, FeSO
_Four・ NH₂O, Fe (ClO_Four)₂・ NH₂O, FeS
O_Four(NH_Four)₂SO_Four・ NH₂O, Fe₃(PO_Four)
₂・ NH₂O, FeCl ₃・ NH₂O, FeF₃・ NH
₂O, Fe₂(SO_Four)₃・ NH₂O, Fe (NO₃)
₃・ NH₂O, Fe (OAc)₃, Fe (ClO_Four)₃
・ NH₂O, FeNH_Four(SO_Four)₂・ NH₂O, Fe
PO_Four・ NH₂O, Fe₂O₃, Fe₃O _Four, Fe (a
cac)₃, Co, CoCl₂・ NH₂O, CoBr₂
・ NH₂O, CoI₂・ NH₂O, CoF₂・ NH
₂O, CoSO_Four・ NH₂O, Co (NO₃)₂・ NH
₂O, Co (OAc)₂・ NH₂O, CoSO_Four(NH
_Four)₂SO_Four・ NH₂O, Co₃(PO_Four)₂・ NH₂
O, CoCO₃, Co (OH)₂, Co (acac)₂
・ NH₂O, Co (acac)₃・ NH₂O, Co₃O
_Four, Ni, NiCl₂・ NH₂O, NiBr₂・ NH₂
O, NiI₂・ NH₂O, NiF₂・ NH₂O, NiS
O_Four・ NH₂O, Ni (NO₃)₂・ NH₂O, Ni
(OAc)₂・ NH₂O, Ni (HCOO)₂・ NH₂
O, Ni (ClO_Four) ₂・ NH₂O, NiSO_Four(NH
_Four)₂SO_Four・ NH₂O, NiCO₃, Ni (O
H)₂, Ni (acac)₂・ NH₂O, NiO, Ni
₂O₃, Cu, CuCl, CuBr, CuI, CuCl
₂・ NH₂O, CuBr₂, CuF₂, CuSO_Four・ N
H₂O, Cu (NO₃)₂・ NH₂O, Cu (OAc)
₂・ NH₂O, Cu (ClO_Four)₂・ NH₂O, Cu
(OH)₂, Cu (OCH₃)₂, Cu₃(PO_Four)₂
・ NH₂O, CuO, Cu₂O, Cu (acac)₂，
Ru, Ru ₃(CO)₁₂, RuCl₂(PPh₃)₃，
RuCl₃・ NH₂O, RuO₂・ NH₂O, Ru
O_Four, Os, OsCl₃・ NH₂O or OsO_Four(This
Here, n usually represents an integer of 0-12. ) Etc.
It is preferable that the iron-based catalyst and the copper-based catalyst have less environmental pollution.
Is mentioned.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B01J 23/74 31/04 31/22 C07B 33/00 7419-4H 41/06 C 7419-4H C07C 27/12 310 8827-4H 29/50 35/37 8827-4H 45/27 7457-4H // C07B 61/00 300

Claims (10)

[Claims] 1. A linear, branched or cyclic alkane having 1 to 20 carbon atoms is reacted with oxygen in the presence or absence of a proton source in the presence of a transition metal catalyst and aldehydes to form an alkane. A method for oxidizing an alkane, which comprises obtaining an alcohol or a ketone corresponding to. 2. A transition metal catalyst is a chromium-based catalyst, a manganese-based catalyst, an iron-based catalyst, a cobalt-based catalyst, a nickel-based catalyst,
The production method according to claim 1, which is a copper-based catalyst, a ruthenium-based catalyst or an osmium-based catalyst. 3. A chromium-based catalyst is Cr, CrCl ₂ · nH ₂ O, Cr
The method according to claim 2, which is Cl ₃ · nH ₂ O, Cr (OAc) ₃ · nH ₂ O or Cr (acac) ₃ . 4. A manganese-based catalyst is Mn, MnCl ₂ .nH ₂ O,
Mn (OAc) ₂ · nH ₂ O, Mn (OAc) ₃ · nH ₂ O, Mn (acac) ₂ · nH ₂ O or Mn (acac) ₃ · nH ₂
The method according to claim 2, which is O 2. 5. The iron-based catalyst is Fe, FeCl ₂ .nH ₂ O, FeCl ₃
-The manufacturing method according to claim 2, which is nH ₂ O, Fe (OAc) ₃ or Fe (acac) ₃ . 6. The cobalt-based catalyst is Co, CoCl ₂ .nH ₂ O,
Co (OAc) ₂ · nH ₂ O, Co (acac) ₂ · nH ₂ O or Co (aca
c) The method according to claim 2, which is ₃ · nH ₂ O. 7. A nickel-based catalyst is Ni, NiCl ₂ .nH ₂ O,
The method according to claim 2, which is Ni (OAc) ₂ · nH ₂ O or Ni (acac) ₂ · nH ₂ O. 8. A copper-based catalyst is Cu, CuCl, Cu (OAc) ₂ · nH ₂
O, Cu (OH) ₂ , Cu (OCH ₃ ) ₂ , Cu ₂ O or Cu (acac) ₂
The method according to claim 2, wherein 9. A ruthenium-based catalyst is Ru, RuCl ₃ .nH ₂ O.
Alternatively, the production method according to claim _2, which is RuO ₂ . 10. The osmium-based catalyst is Os or OsCl ₃
-The manufacturing method according to claim _2, which is nH ₂ O.