JPH02145530A - Production of paraffin based hydrocarbon and/or compound having hydroxyl group - Google Patents

Abstract

PURPOSE:To obtain the title compound in high conversion by bringing an olefin based hydrocarbon compound into contact with an oxygen-containing gas in the presence of a cobalt complex of beta-dicarbonyl compound together with secondary alcohol. CONSTITUTION:An olefin based hydrocarbon compound is brought into contact with an oxygen-containing gas using a compound expressed by formula I [R<1>, R<3>, R<4> and R<6> are H, 1-10C alkyl or formula II (R<7> is alkyl, alkoxy, halogen or CF3; n is 0-5); R<2> and R<5> are R, alkyl, aryl or halogen], e.g. bis(1- pentafluorophenyl-1,3-butanedionato)cobalt as a catalyst in the presence of a secondary alcohol, preferably at 20-100 deg.C for 1-20hr to provide the aimed compound. Even if a raw material compound has a functional group, the functional group is free from decomposition and constitutional ratio of both compounds in reaction product can be controlled by properly choosing reaction temperature, reaction time and amount of secondary alcohol used.

Description

[Detailed description of the invention] Next, the present invention will be specifically explained.

The method for producing a paraffinic hydrocarbon compound and/or a compound having a hydroxyl group according to the present invention involves the production of an olefinic hydrocarbon compound in a system in which a secondary alcohol coexists in the presence of a cobalt complex of a β-dicarbonyl compound described below. This is a method of bringing a compound into contact with an oxygen-containing gas.

First, the catalyst used in the present invention will be explained.

The cobalt complex of the β-dicarbonyl compound used in the present invention can be represented by the following formula [I].

... [I1 In the above formula [I1], RI R3R4 and R6 are each independently an atom selected from a hydrogen atom, an alkyl group having 1410 carbon atoms, and a specific aryl group represented by the following formula [I], or represents a group.

In the above formula [I1, when RI R3R4 and R6 are alkyl groups having 1 to 10 carbon atoms, specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n- -pentyl group, n-hexyl group,
Straight chain alkyl groups such as n-hebutyl, n-octyl, n-nonyl and n-decyl; l-propyl, I-butyl, 5138-butyl,
-butyl group, 2-pentyl group, 3-pentyl group, ne
Alkyl groups having side chains such as o-pentyl group, t-pentyl group, 2-hexyl group and 3-hexyl group; and substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted Examples include alicyclic groups such as a cyclopentyl group, a substituted or unsubstituted cyclooctyl group, and a substituted or unsubstituted adamantyl group. Furthermore, when RSR, R and R6 are alkyl groups, these alkyl groups may be interconnected to form a ring.

Further, when R, R, R and R6 are aryl groups, this aryl group can be represented by the following formula rII].

However, in the above formula [U], R is a lower alkyl group,
Represents a group or atom selected from the group consisting of a lower alkoxy group, a halogen atom, and 10F3, and n is 0 to 5
represents an integer.

In the above formula Cm], when R7 is a lower alkyl group, a preferable alkyl group is an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be linear or branched. Specific examples of such alkyl groups include methyl group, ethyl group, lopropyl group, l-propyl group, n-butyl group, 1-butyl group, 5ec-butyl group and t-butyl group. Can be done.

In addition, in the above formula [nl, when R7 is a lower alkodoxy group, a preferable alkoxy group is an alkoxy group in which the alkyl group constituting this alkoxy group has 1 to 5 carbon atoms, and this alkyl group is a straight chain It may have a shape or a branch.

Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, n-butoxy, I-butoxy, 5ec-butoxy and t-butoxy. be able to.

Furthermore, in the above formula [II], when R7 is a halogen atom, specific examples of the halogen atom include FS
Mention may be made of CD, Br and I.

Note that R7 usually represents a single atom or group, but n
is 2 or more, all R7s do not need to be the same, and the aryl group represented by formula [I1] may have a plurality of different R7s within the scope of the present invention.

Preferred examples of such aryl groups include pentafluorophenyl group, phenyl group, 4-bromophenyl group, 4-fluorophenyl group, 4-trifluorophenyl group, 2.4-dimethoxyphenyl group, 4-methylphenyl group. group, 2.4-dimethylphenyl group, 2.4.8-methoxyphenyl group, l-naphthyl group, and 2-naphthyl group.

In the above formula [I3, R and R5 are each independently an atom or group selected from the group consisting of a hydrogen atom, a lower alkyl group, an aryl group, and a halogen atom.

When R and R5 are lower alkyl groups, preferred alkyl groups are those having 1 to 5 carbon atoms. Specific examples of such alkyl groups include methyl group, ethyl group, n-propyl group, ■-propyl group, n-butyl group,
Mention may be made of 1-butyl, 5ec-butyl and t-butyl.

Further, when R and R5 are aryl groups, preferred aryl groups include phenyl group, 1-naphthyl group and 2-naphthyl group. Note that this aryl group may have a substituent.

Further, when R and R5 are halogen atoms, specific examples of the halogen atoms include FlCjl, Br and I.

The cobalt complex of the β-dicarbonyl compound used in the present invention can be represented by the formula [I1] as described above, but in the cobalt complex represented by the above formula [I], both R and R5 are hydrogen atoms. In this case, when RR3R and R6 are the same group as 4-, this group represents a group other than a methyl group. Therefore, R1R3R4 and R6 do not represent a methyl group at the same time. Similarly, when RI R3R4 and R6 represent the same group, this group is an ethyl group,
Represents a group other than one type of group selected from n-propyl group, 1-propyl group, t-butyl group and aryl group.

Therefore, in this case, this group is the above-mentioned ethyl group, n
-Propyl group,! - It cannot be one type of group selected from propyl group, t-butyl group and aryl group.

Therefore, in the production method of the present invention, a cobalt complex of a β-carbonyl compound as described below is not used.

RI A compound represented by the following formula where R3R4 and R6 are both methyl groups; RI A compound represented by the following formula where R3R4 and R6 are both ethyl groups; RI A compound represented by the following formula where R3R4 and R6 are both l-propyl groups RI A compound represented by the following formula where R3R4 and R6 are both n-propyl groups; RI A compound represented by the following formula where R8R4 and RB are both t-butyl groups; RI A compound where R3R4 and R6 are both phenyl groups A compound represented by the following formula: In addition, in the above formula [I], when R2 and R5 are both hydrogen atoms, when R and R4 are the same group, R and R4 are: ■ phenyl group and when R3 and R6 are the same group, R3 and R6 are groups other than the methyl group. Therefore, in this case, R1 and R4 are both phenyl groups, and R3 and R6 are not methyl groups.

That is, in the production method of the present invention, a cobalt complex of a β-carbonyl compound as described below is not used.

A compound represented by the following formula in which R1 and R4 are both phenyl groups, and R3 and R6 are both methyl groups -
(2) When both are hydrogen atoms, when R and R4 are the same group, this group represents a group other than t-butyl group, and when R and RB are the same group, this group represents a methyl group; Represents a group other than the group. Therefore, in this case, R and R4 are both t-butyl groups, and R and R6 are never methyl groups at the same time.

That is, in the production method of the present invention, R1 and R
are both t-butyl groups, and R3 and R6 are both methyl groups. A cobalt complex of a β-dicarbonyl compound represented by the following formula is used. Furthermore, in the above formula [I], R2 and R5 are also methyl groups. In formula [I],
When R2 and R5 are both chlorine atoms or bromine atoms, and when RI R3R4 and R6 are the same group, this group is a group other than a methyl group.

Therefore, in the production method of the present invention, R2 and R5
A cobalt complex of a β-dicarbonyl compound represented by the following formula in which is either a chlorine atom or a bromine atom, and R1R3R and R6 are both methyl groups, is never used.

Furthermore, in the above formula [I1, when R and R5 are either a methyl group or an ethyl group, RI R
3R and R6 are groups other than methyl. That is,
In this case, when R1R3R and R6 are the same group, these groups cannot be methyl groups at the same time.

Therefore, in the production method of the present invention, a cobalt complex of a β-dicarbonyl compound represented by the following formula in which R2 and R are both methyl groups, and RR3R and R6 are both methyl groups; β-
Specific examples of cobalt complexes of dicarbonyl compounds include compounds of formulas (1) to (20) described below.

(1) Bis(1-pentafluorophenyl-1,
3-butanedionato)cobalt and R2 and R5 are both ethyl, and RIR3R4
A compound represented by the following formula in which both R6 and R6 are methyl groups is never used.

(2) Bis(I-pentafluorophenyl-4,
4-dimethyl-1,3-pentanedionato) cobalt (
4) Bis[I-(4-bromophenyl)-4,4
-dimethyl-1,3-pentanedionato)cobalt(3
) bis(l-phenyl-4,4-dimethyl-1,
3-pentanedionato) cobalt bis(2,4-nonanedionato) cobalt(It) bis[I-(1-adamantyl)-1,3-butanebis(1,3-dicyclohexyl-1,3-prodionato) cobalt cobalt bis(2,2,8,8-atramethyl-4,B-nobis(1,3-butanedionato)) cobalt-1,3-propanedionato] cobalt(14) bis[3-fluoro-2,4-pentanedionato] I,3-di(4-trifluoromethylphenyl)-1,3-propanedionato]cobalt(1B) Bis[I-phenyl-3-(4-trifluoromethylphenyl)-1,3-propanedionato ] Cobalt (15) Bis[I,3-di(4-methoxyphenyl)-1,3-propanedionato] Cobalt (17)
Bis[I-(4-methylphenyl)-3-(4-trifluoromethylphenyl)-1,3-propanedionato]cobalt H3 (18) Bis[I-(4-trifluoromethylphenyl)-3- (2,4,8-trimethylphenyl)-
1,3-propanedionato]cobalt(20) bis(1,2,3-)diphenyl-1,
3-propanedionato]cobalt (19) bis[I-(2,4-dimethoxyphenyl)-3-(4-trifluoromethylphenyl)-i,
a-propanedionato]cobalt'+r3 The above cobalt complexes of β-dicarbonyl compounds can be used alone or in combination.

Note that such a cobalt complex of a β-dicarbonyl compound may be a hydrate or a salt.

In the present invention, the expression "cobalt complex of a β-dicarbonyl compound" also includes hydrates and salts of cobalt complexes of a β-dicarbonyl compound.

For example, as shown below, the cobalt complex of a β-dicarbonyl compound as described above is prepared by adding it to an alcohol solution in which a dicarbonyl compound corresponding to the ligand of the complex to be obtained is dispersed or dissolved, while stirring. It can be obtained by dropping an aqueous sodium hydroxide solution and then adding a cobalt compound such as cobalt chloride to this solution. - is a compound in which R and R4 are the same group.

The cobalt complex of the present invention may be a compound that has symmetry as described above, but it does not need to have symmetry, and compounds that do not have such symmetry may be It is produced by preparing two or more types of cobalt complexes having the same properties, mixing these two or more types of cobalt complexes, and refluxing the mixture in the presence of a reaction solvent such as toluene. The reaction is usually carried out by adjusting the pH value of the reaction solution to an alkaline range of 8 to 12. This reaction is usually performed at O~50
The reaction temperature is 0.1 to 2 hours at a reaction temperature of .degree.

The cobalt complex produced as described above is produced by the above formula [I1, usually with the cobalt atom as the point of symmetry, R1, R625 R, R1 and (hereinafter the blank). As the β-dicarbonyl compound used in this case, any compound that forms a cobalt complex as described above can be used without particular limitation. Specific examples of such β-dicarbonyl compounds include l-pentafluorophenyl-1,3-dicarbonylbutane, ■-pentafluorophenyl-4,4-dimethyl-1,
3-dicarbonylpentane, ■-phenyl-4,4-dimethyl-1,3-dicarbonylpentane, ■-(4-bromophenyl)-4,4-dimethyl-1,
3-dicarbonylbentane, 2,4-dicarbonylnonane, 2,2-dimethyl-3,5-dicarbonylhexane, 1
-(1-adamantyl)-1,3-dicarbonylbutane, 4,6-dicarbonylnonane, 3,7-dimethyl-4,6-dicarbonylnonane, 1.
3-dicyclohexyl-■, 3-dicarbonylpropane, t,a-di(1-adamantyl)-1,3-dicarbonylpropane, 2.2,8.8-tetramethyl-4,6-dicarbonyl Nonane, 3-fluoro-2,4-dicarbonylpentane, 1.3
-dicarbonylbutane, 1,3-di(4-fluorophenyl)-1,3-dicarbonylpropane, 1,3-di(4-trifluoromethylphenyl) -1
,3-dicarbonylpropane, t,a-di(4-methoxyphenyl)-1,3-dicarbonylpropane, ■-phenyl-3-(4-)lifluoromethylphenyl)-1,3-dicarbonylpropane, ■-(4-methylphenyl)-3-(4-)lifluoromethylphenyl)
-1,3-dicarbonylpropane, -(4-trifluoromethylphenyl)-3-(2,4,6 trimethylphenyl)-1,3-dicarbonylpropane, 1-(2,4-dimethoxyphenyl) )-3-(4-trifluoromethylphenyl)-1,3-dicarbonylpropane, and 1,2,3-triphenyl-1,3-dicarbonylpropane. These β-dicarbo.

The nil compounds can be used alone or in combination.

Cobalt compounds used to produce cobalt complexes with β-dicarbonyl compounds as mentioned above include, for example, inorganic cobalt compounds such as CoC(12) and organic cobalt compounds such as Co(CH3COO)2. These cobalt compounds can be used alone or in combination.

Although this reaction between the β-dicarboxylic acid and the cobalt compound can be carried out in water, it is preferable to carry out the reaction in a mixed solvent system of water and alcohol. In this case, the weight ratio of water and alcohol in the mixed solvent used is
Usually within the range of 10:90 to 100:0.

The production method according to the present invention uses a cobalt complex of a β-carbonyl compound as described above. In,
It is characterized in that an olefinic hydrocarbon compound and an oxygen-containing gas are brought into contact in the presence of the above-mentioned β-dicarbonyl compound.

The olefinic hydrocarbon compound used in the present invention is usually an olefinic hydrocarbon compound having 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms, for example, the following formula [I[I]
It can be expressed as

However, in the above formula [I11], R8 is one group selected from an alkyl group, an aryl group, a cycloalkyl group, and an arylalkyl group, and RR10 and R11 are each independently a hydrogen atom or an alkyl group. ,
It is a group selected from an aryl group and an alkylaryl group. Incidentally, these R8R9R and R11 may be the same group, or may be different groups.

Such olefin hydrocarbon compounds represented by the above formula [I11] include aromatic olefin hydrocarbon compounds, alicyclic olefin hydrocarbon compounds, and aromatic olefin hydrocarbon compounds.

Furthermore, these compounds may have a substituent.

Furthermore, the double bond that reacts in the method of the present invention may be located at the end of the main chain, or may be located at a portion other than the end, for example, near the center of the main chain, and may also be located at the end of the side chain ( It may be located at the exo-terminus), or it may be located at a portion other than the end of the side chain, for example, near the center of the side chain.

The olefinic hydrocarbon compound used in the present invention is usually a compound having one double bond that is active in the reaction of the present invention, as shown in the above formula [I11]. , compounds having two or more such double bonds can also be used.

Furthermore, when it has two or more double bonds, these double bonds do not need to exhibit the same activity in the reaction of the present invention.

Specific examples of olefinic hydrocarbon compounds used in the present invention include ethylene, propylene, l-butene, 2-butene, isobutyne, ■-pentene, 2-pentene, 2-methyl-1-butene, -Methyl-1-butene, 2-methyl-2-butene, ■-hexene, 2,3
- Aliphatic olefinic hydrocarbon compounds such as dimethyl-2-butene, ■-heptene, ■-octene, l-nonene, ■-decene, 5-decene and 2-methyl-2-decene; cyclopentene, cyclooctene, cyclohexene and alicyclic olefin hydrocarbon compounds such as cycloheptene; 4-phenyl-1-butene, 4-phenyl-2-butene 2-methyl-4-phenyl-1-butene, stilbene,
Aromatic olefinic hydrocarbon compounds such as styrene and 5-phenyl-3-methyl-2-pentene can be mentioned. Furthermore, in the method of the present invention, in addition to the above-mentioned olefinic hydrocarbon compounds, olefinic hydrocarbon compounds having functional groups can also be used. Examples of the above-mentioned olefinic hydrocarbon compounds that can be used in the present invention include olefinic alcohols such as allyl alcohol, crotyl alcohol, allylcarbinol, citronellol, phytol and cinnamyl alcohol; acrolein, crotonaldehyde, Olefinic aldehydes such as tiglinaldehyde, citronellal and cinnamaldehyde; acrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, methacrylic acid, eigeric acid, tiglic acid, allyl acid, β, β-dimethylacrylic acid, hydrosorbic acid, isoturpon acids, olefinic carboxylic acids such as pyroterpic acid, tellarinic acid, undecylic acid, oleic acid, elaidic acid, ericic acid, brassic acid, cinnamic acid, and allocinnamic acid; and methyl vinyl ketone, ethylidene acetone, mesityl oxide, allyl Olefin ketones such as methyl ketone, allyl acetone, methyl heptene, benzylidene acetone and chalcone; substituted aromatic olefin hydrocarbon compounds such as allyl benzoate, allyl benzoate, crotyl benzoate and allyl benzyl ether.

Even if an olefinic hydrocarbon compound having such a functional group is used, according to the production method of the present invention, a compound having a hydroxyl group and/or a paraffinic hydrocarbon compound can be produced without affecting the functional group. can do.

In the method for producing a compound having a hydroxyl group and/or a paraffinic hydrocarbon compound of the present invention, an olefinic hydrocarbon compound as described above is brought into contact with an oxygen-containing gas in the presence of a secondary alcohol.

Examples of secondary alcohols that can be used here include isopropyl alcohol, 5eC-butanol, 3
- Aliphatic secondary alcohols such as pentanol and 2-pentanol; Aromatic secondary alcohols such as benzhydrol and α-phenylethyl alcohol; and alicyclic secondary alcohols such as cyclohexanol, cyclopentanol, and cycloheptatool. alcohols. Such secondary alcohols can be used alone or in combination.

Among the secondary alcohols mentioned above, in the present invention, isopropyl alcohol, cyclopentanol or 5ee
- Particular preference is given to using butanol.

As the oxygen-containing gas used in the present invention, not only oxygen itself can be used, but also a gas containing components other than oxygen such as air can also be used. When using a gas containing components other than oxygen, a gas in which the concentration of oxygen in the gas is 5% by volume or more is preferably used in consideration of the economic efficiency of the reaction.

In the method for producing a paraffinic hydrocarbon compound and/or a compound having a hydroxyl group according to the present invention, the cobalt complex of the β-carbonyl compound is usually 0.005 to 0.0% per mole of the olefinic hydrocarbon compound used.
It is used in a proportion of 5 mol, preferably within the range of 0.01 to 0.2 mol.

Further, the amount of secondary alcohol is usually 100 to 100 parts by weight per 100 parts by weight of the olefinic hydrocarbon compound used.
00 parts by weight, preferably in the range of 300 to 5000 parts by weight.

Furthermore, the oxygen-containing gas introduced into the reaction system is usually introduced in excess of the olefinic hydrocarbon compound used.

The above reaction is desirably carried out at a reaction temperature of 0 to 150°C, preferably 20 to 100°C. By carrying out the reaction at such a temperature, the reaction is usually completed in 0.5 to 30 hours, preferably 1 to 20 hours. Further, this reaction can be carried out in any state of reduced pressure to increased pressure, and is particularly preferably carried out in a state of normal pressure to increased pressure.

The above reaction can be carried out in various forms such as fixed bed, fluidized bed, moving bed, etc.

By reacting in this manner, the olefinic hydrocarbon compound becomes a paraffinic hydrocarbon compound and/or a compound having a hydroxyl group corresponding to the olefinic hydrocarbon compound used.

For example, when using an olefinic hydrocarbon compound represented by the above formula [I11], the following formula [IV]
A paraffinic hydrocarbon compound represented by formula [V] and/or a compound having a hydroxyl group represented by formula [V] can be obtained.

R10′″\R11... [V] However, in the above formulas [IV] and [V], R8R
9R and Rit have the same meaning as O 2 as in [I1r] above, one of R and R13 is a hydroxyl group, and the other represents a hydrogen atom.

That is, for example, as an olefinic hydrocarbon compound, l
When -decene is used, either or both of n-decane and 2-decanol are produced. Note that, accompanying this reaction, a corresponding ketone is usually produced as a by-product. For example, in the example above, it is 2-decanol.

In the production method of the present invention, the production ratio of the paraffinic hydrocarbon compound to the compound having a hydroxyl group can be controlled by controlling the type of cobalt complex of the secondary alcohol and β-carbonyl compound used, reaction temperature, reaction time, etc. This can be done by changing. For example, focusing on the reaction time among the above conditions, if the same catalyst is used, the longer the reaction time, the higher the production ratio of compounds having hydroxyl groups will often be. Furthermore, when focusing on the reaction temperature, if the same catalyst is used, the production ratio of compounds having hydroxyl groups often increases as the reaction temperature increases.

Furthermore, as the amount of secondary alcohol used increases, the production ratio of compounds having hydroxyl groups tends to increase.

Furthermore, by using the cobalt complex of a β-carbonyl compound as described above and selecting the type of secondary alcohol, the conversion rate of the olefinic hydrocarbon compound used as a raw material can be increased to 40% or more. moreover,
By setting suitable reaction conditions, this conversion rate can be increased to 7.
It can be set to 0% or more.

Effects of the Invention According to the present invention, since a novel cobalt complex as described above is used as a catalyst, a compound having a hydroxyl group and/or a paraffinic hydrocarbon compound can be efficiently produced from an olefinic hydrocarbon compound. Can be done.

That is, according to the method of the present invention, since the reaction is not an equilibrium reaction, a compound having a hydroxyl group and/or a paraffin group can be converted at a high conversion rate without performing a complicated operation such as removing the reaction product from the reaction system. Hydrocarbon compounds can be produced.

Moreover, even if the olefinic hydrocarbon compound has a functional group, the functional group will not be decomposed, and therefore, the olefinic hydrocarbon compound having a functional group can be converted into a paraffinic hydrocarbon having such a functional group. A hydrogen compound and/or a compound having a hydroxyl group can be produced.

Furthermore, by adjusting the reaction conditions, it is also possible to adjust the ratio of the produced paraffinic hydrocarbon compound to the compound having a hydroxyl group.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 Production of bis(1-pentafluorophenyl-1,3-butanedionato)cobalt(II) ■-Pentafluorophenyl-1,3-butanedione 0
．． To a mixture of 945 g (3.75 mmol), 20 ml of water and 10 ml of methanol was added 1.875 ml of a 2M aqueous sodium hydroxide solution with stirring at room temperature.
It was dripped in minutes.

After stirring this mixture at room temperature for 30 minutes, a solution of 0.45 g of cobalt chloride hexahydrate dissolved in 5 ml of water was added, and the mixture was further stirred for 30 minutes.

After 30 minutes, the precipitated crystals were collected by filtration, washed with 10 ml of water, and dried at 70°C under reduced pressure to give a 0.
96 g of bis(l-pentafluorophenyl-1,3-
Butanedionato)cobalt (n) was obtained. (Yield 91%
) The properties and physical properties of this cobalt complex are as follows.

Properties: Pink crystal Melting point 163-166°C Infrared absorption spectrum (KBr tablet method, cffi-1)
2968, 1646, 1498, 1428.1382,
1123, 1085, 982 mass spectrum m/e 561 (M) A chart of the infrared absorption spectrum of the obtained cobalt complex is shown in FIG.

Reference Examples 2 to 20 In Reference Example 1, ■-pentafluorophenyl 1.
Formulas (2) to (
A cobalt complex shown in 20) was produced.

Crystal state, melting point, m/e of the obtained cobalt complex
, and the yields are also listed in Table 1. In addition, the charts of the IR spectrum of the obtained cobalt complex are shown in Figures 2 to 20.
As shown in the figure.

Reference Example 21 (1-Pentafluorophenyl-1,3-butanedionato) (1-phenyl-1,3-butanedionato) Production of cobalt(II) In Reference Example 1, ■-pentafluorophenyl-1.
Instead of 3-butanedione, ■-phenyl 1.3~
Bis(l-phenyl-1,3-butanedionato)cobalt(II) was prepared in the same manner except that butanedione was used.

150 mg of the obtained bis(1-phenyl-1,3-butanedionato)cobalt (II) and 220 mg of bis(1-pentafluorophenyl-1,3-butanedionato)cobalt (■) obtained in Reference Example 1 were added. , and refluxed for 3 hours in 30 ml of toluene.

After refluxing, 379 mg of (
1-Pentafluorophenyl-1,1-butanedionato)(1-phenyl-1,3-butanedionato)cobalt (■) was obtained (yield, 100%).

The melting point of the obtained cobalt complex is 75-78 °C, and the m/e value measured by mass spectrometry is 471 (M
)Met.

I of the obtained cobalt complex measured by KBr tablet method
A chart of R is shown in FIG.

As is clear from Figure 21, 1652 cm-'15
95cm 1561cm 1510cm-'1
401 am 1316 cm 1274 c
m-1-■-1 1235cm 1096 cm 991 am
-' and 7740m-' specific absorptions are seen.

Example 1 140 mg (1.0 mmol) of 1-decene and 5.0 ml of isopropanol were mixed, and Reference Example 1 was added to this mixture.
Bis(1-pentafluorophenyl-1,3
-butanedionato)cobalt(II) 112 mg (0,
2 mmol) was added. The content of cobalt complex in this mixture is 20 mol % based on -decene.

This mixture was brought into contact with oxygen at a pressure of 1 atmosphere and allowed to react at 75° C. for 2.5 hours.

When the obtained reaction solution was analyzed by gas chromatography, the yield of 2-decanone was 13%, the yield of 2-decanol was 77%, and n-decane was not produced. Moreover, the conversion rate of l-decene was 100%.

Examples 2-19 In Example 1, instead of bis(l-pentafluorophenyl-1,3-butanedionato)cobalt(II), the cobalt complexes listed in Table 2 were used in the amounts listed in Table 2, Further, the reaction was carried out in the same manner except that the type of secondary alcohol was changed as shown in Table 2, and the reaction conditions were changed as shown in Table 2.

The yield of the reaction product is also shown in Table 2.

Example 20 1-decene 140 mg (1.0 mmol), Reference Example 21
A mixture of 94 mg (0.2 mmol) of (l-pentafluorophenyl-1,3-butanedionato)(1-phenyl-1,3-butanedionato)cobalt(II) prepared in
s The reaction was carried out at a reaction temperature of 75°C.

Next, the reaction solution was analyzed using gas chromatography.

As a result, the yield of 2-decanol was 63%, and the yield of 2-decanol was 63%.
The yield of decanone was 19%.

Comparative Example 1 140 mg (1.0 mmol) of 1-decene, bis(3-
Chloro-2,4-pentanedionato)cobalt(II)
52 mg (0,2 mmol) and isopropanol 5
ml of the mixture at an oxygen pressure of 1 atm s and a reaction temperature of 75°C.
I reacted with

Next, the reaction solution was analyzed using gas chromatography.

As a result, the yield of 2-decanol was 4% and the yield of 2-decanone was 1%.

Examples 21 to 22 Example 1 except that 5-decene was used instead of l-decene, 10 mol% of the cobalt complex listed in Table 3 was used, and the reaction time was as listed in Table 3. The reaction was carried out in the same manner.

Next, the reaction solution was analyzed using gas chromatography.

Example 23 The conversion rate of 5-decene and the yields of n-decane, 5-decanone and 5-decanol are listed in Table 3. In Example 1, 2-methyl-
The cobalt complexes listed in Table 4 were prepared using 2-decene.
The reaction was carried out in the same manner except that 0 mol% was used and the reaction time was as shown in Table 4.

Next, the reaction solution was analyzed using gas chromatography.

The conversion rate of 2-methyl-2-decene and the yield of 2-methyldecane and 2-methyl-2-decanol are listed in Table 4.

[Brief explanation of the drawing]

Figure 1 shows bis(l-pentafluorophenyl-1,3
1 is a chart of an IR spectrum of cobalt (butanedionato). Figure 2 shows bis(l-pentafluorophenyl-4,4
-dimethyl-1,3-pentanedionato) cobalt I
It is a chart of R spectrum. Figure 3 shows bis(■-phenyl-4,4-dimethyl-1
, 3-pentanedionato) cobalt. Figure 4 shows bis[I-(4-bromophenyl)-4,
4-dimethyl-1,3-pentanedionato) of cobalt! It is a chart of R spectrum. FIG. 5 is a chart of the IR spectrum of bis(2,4-nonanedionato)cobalt. Figure 6 shows bis[I-(1-adamantyl)-1,3
FIG. 2 is a chart of an IR spectrum of cobalt (butanedionato). FIG. 7 is a chart of the IR spectrum of bis(3,7-dimethyl-4,6-nonanedionato)cobalt. Figure 8 shows bis(1,3-dicyclohexyl-1,3-
1 is a chart of an IR spectrum of cobalt (propanedionate). Figure 9 shows bis[I,3-di(1-adamantyl)-1
, 3-propanedionato] is a chart of the IR spectrum of cobalt. Figure 10 shows bis(2,2,8,8-tetramethyl-4
, 6-nonanedionato) is a chart of the IR spectrum of cobalt. FIG. 11 is a chart of the IR spectrum of bis[3-fluoro-2,4-pentanedionato]cobalt. FIG. 12 is a chart of the IR spectrum of bis(1,3-butanedionato)cobalt. FIG. 13 is a chart of the IR spectrum of bis[I,3-di(4-fluorophenyl)-1,3-propanedionato]cobalt. FIG. 14 is Char 1 of the IR spectrum of bis[l,3-di(4-trifluoromethylphenyl)-1,3-propanedionato]cobalt. FIG. 15 is a chart of the IR spectrum of bis[I,3-di(4-methoxyphenyl)-1,3-propanedionato]cobalt. FIG. 16 is a chart of the IR spectrum of bis[I-phenyl-3-(4-trifluoromethylphenyl)-1,3-propanedionato]cobalt. Figure 17 shows bis[I-(4-methylphenyl)-3-
It is a chart of the IR spectrum of (4trifluoromethylphenyl)-1,3-propanedionato]cobalt. Figure 18 shows bis[I-(4-trifluoromethylphenyl)-3-(2,4,6-)limethylphenyl)-1
, 3-propanedionato] is a chart of the IR spectrum of cobalt. Figure 19 shows bis[I-(2,4-dimethoxyphenyl)-3-(4-)lifluoromethylphenyl)-1,3
-Propanedionate] of cobalt! It is a chart of R spectrum. Figure 20 shows bis(1,2,3-triphenyl-1,3
-Propanedionate] is a chart of the IR spectrum of cobalt. Figure 21 shows (1-pentafluorophenyl-1,3-
1 is a chart of the IR spectrum of cobalt (1-phenyl 1,3-butanedionato). agent

Claims (1)

[Claims] (1) It is characterized by bringing an olefinic hydrocarbon compound into contact with an oxygen-containing gas in the presence of a cobalt complex of a β-dicarbonyl compound represented by the following formula [I] and in the coexistence of a secondary alcohol. Method for producing paraffinic hydrocarbon compounds and/or compounds having hydroxyl groups; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the above formula [I], R^1, R^3, R^ 4 and R^6 each independently represent a hydrogen atom, a carbon number of 1 to 1
0 alkyl group (however, these alkyl groups may be connected to each other to form a ring) and an aryl group represented by the following formula [II]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・[II] (However, in the above formula [II], R^7 is a lower alkyl group, a lower alkoxy group, a halogen atom, and -CF_
represents a group or atom selected from the group consisting of 3, and n
represents an integer from 0 to 5), and R^2 and R^5 each independently represent a hydrogen atom,
Represents an atom or group selected from the group consisting of a lower alkyl group, an aryl group, and a halogen atom; (However, in the above formula [I], when R^2 and R^5 are both hydrogen atoms, R^1 , R^3, R^4 and R^6
represent the same group, the group is a group other than methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group or phenyl group, and R^2 and R^
When both 5 are hydrogen atoms, when R^1 and R^4 are the same group, and when R^3 and R^6 are the same group, R^1 and R^4 are is a group other than a phenyl group, and R^3 and R^6 are groups other than a methyl group, and furthermore, when R^2 and R^5 are both hydrogen atoms, R^1 and R^4 are the same groups, and R^3 and R^6 are the same, R^1 and R^4 are groups other than t-butyl, and R^3 and R^6
is a group other than a methyl group, and furthermore, when R^2 and R^5 are either a chlorine atom or a bromine atom, R^1, R^
3. When R^4 and R^5 are the same group, the group is a group other than a methyl group, and both R^2 and R^5 are either a methyl group or an ethyl group. In the case, R^1, R^3, R
When ^4 and R^6 are the same group, the group is a group other than a methyl group)].