JPH03204843A - Production of aminoanthraquinone - Google Patents

Abstract

PURPOSE:To obtain the subject substance in high yield by reacting nitroanthraquinone with CO and water in liquid phase using a homogeneous catalyst system consisting of a Rh compound of Ru compound and a solvent optionally in the presence of an amine compound. CONSTITUTION:Aminoanthraquinone is produced by reacting nitroanthraquinone with CO and water. In the above reaction, the nitro group can selectively be reduced to amino group by using a homogeneous catalyst system consisting of a Rh compound or Ru compound [e.g. Rh4(CO)12 or Ru3(CO)12] and a solvent (e.g. methanol). The catalytic activity of the above catalyst can remarkably be improved by carrying out the reaction in the presence of an amine compound (e.g. trimethylamine). Further remarkable improvement of the catalytic activity can be achieved by using a homogeneous catalyst system consisting of a Ru compound and a solvent together with an amine compound and a copper compound (e.g. cupric oxide).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing aminoanthraquinone from nitroanthraquinone, particularly 1-aminoanthraquinone from 1-nitroanthraquinone.

More specifically, the present invention relates to a method for producing aminoanthraquinone, which comprises reacting nitroanthraquinone with carbon monoxide and water in a liquid phase using a homogeneous catalyst consisting of a ruthenium compound or rhodium compound and a solvent.

Aminoanthraquinones, including 1-aminoanthraquinone, are industrially important compounds as intermediates for anthraquinone dyes.

[Conventional technology]

Conventionally, 1-aminoanthraquinone has been produced by a method in which anthraquinone is sulfonated and then aminated, and an anthraquinone is nitrated and then reduced.

Methods for reducing nitroanthraquinone related to the present invention include reduction using metal powder such as iron powder in an acidic medium such as sulfuric acid, reduction using alkali sulfide, hydrosulfide, hydrazine, glucose, etc., and reduction using ammonia. There are a method of amino substitution by reacting with a hydrogen atom, a method of catalytic hydrogenation using palladium-carbon, etc.

Further, methods for producing aromatic amine compounds from aromatic nitro compounds using -carbon oxide and water include, for example, (1) Journal of the American Chemical Society (J, Am, Chem, Soc, 1978 ．j
43969) contains tetrahydrofuran-trimethylcyamine water in the presence of a rhodium or ruthenium catalyst. Liquor liquid? An example of a reduction reaction of nitrohenzene carried out in a medium.

(2) European Patent Publication No. 0097592 discloses an example in which a chelating amine such as phenanthroline was added to a rhodium or ruthenium catalyst in an ethanol solvent to perform a reduction reaction of nitrohenzene, nitrotoluene, etc.

However, none of these discloses a method for producing aminoanthraquinone from nitroanthraquinone using carbon oxide and water.

[Problem to be solved by the invention]

The method of sulfonating anthraquinone and then aminating it has problems not only in the toxicity of the catalyst used, that is, the mercury compound, and in the treatment of wastewater, but also in low yield and reaction rate.

In addition, in the method of reducing nitroanthraquinone obtained by nitration of anthraquinone, for example, in the stoichiometric reduction method using a sulfide such as hydrosulfide, it is necessary to treat by-product inorganic salts. This also has the disadvantage of causing problems such as inorganic salts being mixed into the liquid. On the other hand, the reduction reaction using palladium-carbon powder involves various side reactions such as reducing not only nitro groups but also ketone groups (carbonyl groups), which reduces the yield of the desired product, aminoanthraquinone. do. Furthermore, there are many economical disadvantages, such as the fact that separation from the catalyst requires a great deal of effort.

In addition, in the method of reducing aromatic nitro compounds using -carbon oxide and water, in the ruthenium-trimethylamine aqueous solution catalyst system of (1) above, a considerably large amount of trimethylamine (103 times as much as ruthenium metal) is used for the reduction reaction of nitrohenzene. degree).

Furthermore, in the above catalyst system, the water gas shift reaction that generates hydrogen and carbon dioxide from carbon oxide and water proceeds at a considerable speed simultaneously with the reduction reaction of the nitro group, so a large amount of hydrogen is produced as a by-product in the reaction system. As a result, there was a problem that large amounts of water and carbon monoxide were also consumed in addition to the reduction reaction. In addition, in the rhodium or ruthenium-chelating amine catalyst system described in (2) above, only compounds with a substituent that is inert to the reduction reaction such as an alkyl group, an alkoxy group, or an amino group are effective as nitro compounds. It is stated that.

(Means for Solving the Problems) In view of the above circumstances, the present inventors have repeatedly investigated the reaction of carbon monoxide and water with aromatic nitro compounds in the presence of a homogeneous catalyst in the liquid phase. By using a homogeneous catalyst consisting of a rhodium compound or ruthenium compound and a solvent, the reaction not only exhibits high catalytic activity, but also has a high selectivity of almost 100%, retaining the anthraquinone skeleton and only nitro groups. discovered that aminoanthraquinone can be obtained from nitroanthraquinone with a so-called nitro group selectivity of almost 100%,
After further various studies, the present invention was completed.

That is, the present invention is characterized in that nitroanthraquinone is reacted with -carbon oxide (hereinafter abbreviated as CO) and water in a liquid phase using a homogeneous catalyst consisting of a rhodium compound or a ruthenium compound and a solvent. The present invention provides a method for producing aminoanthraquinone.

The present invention also provides a method for producing aminoanthraquinone by reacting nitroanthraquinone with CO and water in the presence of an amine compound in a homogeneous catalyst consisting of a rhodium compound or ruthenium compound and a solvent. .

Furthermore, the present invention uses a homogeneous catalyst consisting of a ruthenium compound and a solvent, and allows nitroanthraquinone to react with CO and water in a liquid phase, in the presence of an amine compound, and in the presence of a copper compound. The present invention provides a method for producing aminoanthraquinone characterized by the following.

The present invention will be explained in detail below.

When 1-nitroanthraquinone, for example, is used as the nitroanthraquinone, this reaction is presumed to consist of the following formula. Three times the mole of CO is required for the nitro group, and as a result, carbon oxide is produced as a by-product.

1-2) 07 Anthraquinone
1-Aminoanthraquinone In the reaction of the present invention, Co/)120 is used as a hydrogen source.

In the present invention, nitroanthraquinone is a compound having one or one nitro group in the anthraquinone skeleton, specifically 1-nitroanthraquinone, 2-nitroanthraquinone,
Nitroanthraquinone, 12-11.3-11,4-1
1.5-11, 61.7-11, 8-12.3-12,
6-127-1, and mixtures thereof. For example, for industrial use,
A nitration mixture containing 1-nitroanthraquinone obtained by mononitrating anthraquinone as a main component and dinitroanthraquinone or the like as a subcomponent, or a highly purified 1-nitroanthraquinone obtained by purifying the same is preferred.

The homogeneous catalyst used in the present invention refers to one in which a rhodium compound or a ruthenium compound as a catalyst is partially or completely dissolved in the above-mentioned solvent.

The catalyst used in the present invention is a rhodium compound or a ruthenium compound, which forms a complex with a carbonyl ligand, a compound that forms a rhodium carbonyl complex or a ruthenium carbonyl complex in the reaction system, or a complex with phosphine or phosphite. Compounds that do are preferred.

For example, carbonyl compounds, acetylacetonate salts,
Examples include salts and coordination compounds such as carboxylates, oxides, hydroxides, halides, nitrates, and phosphates.

In addition, when forming a complex with phosphine or phosphite, the following format (n), (I[[), (, TV
) RhX(Co), (PP3)3-, (II) RuH
, IYz-(Co)-(PRz)n-p (m
)Ru(Co)r(PRz)s-r
([V) (wherein, X is hydrogen), element, chlorine, bromine,
Represents iodine, Y represents fluorine, chlorine, bromine, iodine, PP3 represents pph, PEtPhz, PEtz
PhP (OPh) represents 3, n is an integer from 0 to 3,
m represents an integer of 0 to 2, p represents an integer of 0 to 4, and r represents an integer of 0 to 5, respectively. ) that generates the complex shown in the reaction system.

Specifically, Rh (Co) z (a
cac) + [RhCI (COD)]□, Rh4
(Co)+□, Rh6(CO), [Rh(Co)
zc]] z, Rt+z(OAc) a, Rh(acac
)+, RhzO:+Rho□・2H20,RhzO3
・5HzO, Rh(No:+)s, Rh1(SOa)
3RhCIs+RhBr1+Rhl++ RhH(PP
b+)3. RhF(PPt++)iRhCI(PPh
3) 3. RhBr(PPh3) 3+ Rh1(P
Pl+s) ff+RhH(Co) (PPt++)
Z+l? hF (Co) (PPh3) 2 , R
hC1(Co) (PPh,) tRhBr (Co)
(PPh 3) Z, RhI (Co) (PPh
s) t, RhH(Co) t (PPh 3).

RhF(CO)! (PPhff), RhCI(CO)
z(PPhi)RhBr(Co)z(PPh+) Rh
I(Co)z(PPh+), RhH(PEtPhz)
3RhF (PEtPhz) + IRhCI (PEtPhz
)s, RhBr(PEtPhz)i.

Rh1(PEtPhz)z, RhH(Co)(PE
tPhri2RhF(Co)(PEtPhz)z, R
hCI(Co)(PEtPhz)zRhBr(CO)(
PEtPhz)z, Rh1(Co)(PEtPhz)z
RhH(Co)z(PEtPhz), RhF(Co
)z(PEtPhz)RhCI(Co)z(PEtPhz
z), RhBr(Co)z(PEtPt+z).

Rh+(Co)z(PEtPhz), I? hH(PEt
2Ph)ff.

RhF(PEtzPh)z, RhCI(PEtzP
h) i, RhBr(PEtzPh)3Rhl(PEtz
Ph)z, RhH(Co)(PEtzPh)zRh
F(CO)(PEtzPh)z, RhCI(Co)(P
EtzPh)zRhBr(CO) (PEtzPh)
Z, Rh1(Co) (PEtzPh) zRhH(
CO)z(PEtzPh), RhF(CO)z(PEt
zPh)RhCI(Co)z(PEtzPh), RhB
r(Co)z(PEtzPh)Rh+(Co)z(PE
tzPh), RhH(PEt:+)i, RhF
(PEt3)3゜RhCl (PEt:+) 3+ R
hBr(PEta)! , Rh+(PE++) yR
h) I(Co)(PEt3)! , RhF(Co)(
PEt3)2RhCI (Co) (PEt3) 2.
RhBr (CO) (PEt*) 2Rh+(Co
)(PEt3)z, RhH(Co)z(PEtz)
RhF(CO)z(PEt:+), RhCI(Co)z
(PEtz)RhBr(CO)z(PEt3), Rh+
(CO)z(PEts).

RhH (P (OPh) 5> ++ RhF (P
(OPh) 3>3. RhCl (P(OPh)
3) ff+RhBr(P(OPh)3)3. Rh1(
P(OPh)z)3RhH(Co) (P(OPh)
3) Z, RhF (CO) (P (OPh)
3)! RhCI(Co)(P(OPh)i)z,R
hBr(CO)(P(OPh)z)zRh+(Co)(
P(OPh)3)z, RhH(CO)z(P(OPh)
z) RhF (Co) z (P (OPh) :+)
, RhCl (Co) 2 (P (OPh) 3
)RhBr(CO)z(P(OPh):+), Rh1(
Co)z(P(OPh)*)Ruz(Co)+z,
H4Ru4(CO)+z, [RuC1z(COD)]-
.

[RuHCI, (GO) 312+ Ru (Go)
S+ Ru0z+ RuCI=, RuBr3+ R
ul 3Ru(acac)a, Ru(No)(NO3)
*, Ru(No)C13゜HJu(SOz)zOH,R
uHz(PPl'+s)4. RuHz(Co)(PPh
3) i.

Rut(z(GO)z(PPhi)zl RuHz(C
O)s(PPhi), RuL(CO)-RuHCI (
PPhz) a, RuHCl (Co) (PPl
++) 1IRuHCI(GO)z(PPhs)z, R
uHCI(CO)s(PPhx).

RIIHCI(Co)4. RuC1z(PPII3)4
．． RuCIz(CO)(PP)++)+RuCIz(C
o)z(PPh3)z, RuC1z(Co)+(PPh
z) RLIC12(Co)4. RuHBr(PPh+)
4. RuHBr(Co)(PPh3)sRullBr(
Co)z(PPhx)z, RuHBr(CO)+(PP
h*).

RuHBr(Co)4. RuBrz(PPh3)alR
uBrz(Co)(PPh+)IRuBrz(CO)z
(PPhs)z, RuBrz(CO)s(PPha)I
RuBrz(CO)n, RuHI(PPh3)n, R
uHI(CO)(PPht):+1RuH1(Co)z
(PPh3)z, RuHl(Co)3(PPh+),
Ru[(Co)sRulz(PPh:+)a, Ru1z
(Co) (PPhz) iRulz (CO)z (PPhz
)z, Ru1z(Co)z(PPh3), Ru1z
(Co)4Ru)It(PEtPhz) a, Ru1
(z(Co) (PEtPhz) !RuHz(Co)
z(PEtPhz)z, Ru)lz(CO)z(P
EtPhz).

RuHCl (PEtPhz) a, RuHCl (
Co) (PEtPhz) 3RuHCI(CO)z(
PEtPhz)z, RuHCl(Co)3(PEtPh
z) RuCIz(PEtPhz)a, RuCIz(CO
) (PEtPhz)ff.

RuC1z(CO)z(PEtPhz)z, RuCIz
(Go):+(PEtPhz).

RuHBr(PEtPhz)a, RuHBr(Go)
(PEtPhz)sRuHBr(CO)z(PEtPhz
z)z, RuHBr(CO)3(PEtPhz)RuB
i(PEtPhzlj, RuBrz(Co) (PEt
Phz)zRuBrz(CO)z(PEtPhz)z,
RuBrz(CO)z(PEtPhz).

RuHI(PEtPhz) a, RuHI(Co)
(PEtPhz) 3IRuHI(CO)z(PEtP
hz)z, RuHI(COh(PEtPht)Rul
z(PEtPhz) a, Ru1z(Co) (PE
tPhz) 3゜Ru1l(CO)t(PEtPhz)
z, Ru1z(CO)2(PEtPhz)lRuHz(
P(OPh)3)n, RuHz(Co)(P(OP
h)i)sRung (Co)! (P (OPh)
3) 2, RuHz (Co) s (P (O
Ph) s).

RuHCl (P(OPh) 3) 4+ RuHCl
(Co) (P(OPh) s) s.

Ru1lCI(Co)z(P(OPh)z)z, R
uHCl(Co)+(P(OPh):+)RuCIz(
P(OPh):+)n, RuC1z(CO)(P(OP
h)z)+.

RuC1z(Co)z(P(OPh)3)z, Ru
C1z(Co)3(P(OPh)3)RuHBr(P
(OPh) i) a, RuHBr (CO)
(P (OPh) i) 5RuHBr (Co) 2
(P (OPh) 3) Z, Rut(Br
(Co) 3 (P (OPh) 3) RuBr2 (P
(OPh)t)n, RuBrz(CO) (P(OPh
)3)3RuBrz(Go)z(P(OPh):+)z
, RuBrz(Co)i(P(OPh)3)Rul
(I(P(OPh)+)4. RuHI(CO)(P
(OPh)+):+.

RuHI (Co) t (P (OPh) 3) z
, RuHI (Co) z (P (OPh) 3
) Rurz(P(OPh)+)4. Rurz (CO
)(P(OPh)x)z.

Ru1z (Co) 2 (P (OPh) s) 2
．． Ru1z (Co) 3 (P (OPh) 3)
Ru(Co) a (PP)++), Ru(CO)
x (PPt++) 2+ Ru (Co) 2 (
PPh*) 3Ru(CO)(PPha)a, Ru(P
Phz)s, Ru(Co)a(PEtPhz)Ru(C
O) 5(PEtPhz) z, Ru(Co) z(P
EtPhz)3Ru (Co) (PEtPhz) 4
．． Ru (PEtPhz) S, Ru (Co)
s (P (OPh) 3).

Ru (Co) 3 (P (OPh) 3)! ,
Ru (Co) z (P (OPh) 3)! R
u(Co)(P(OPh)+)4. Ru(P(OPh
)z)s etc.

Among these, Rhn(Co)+t, Rb6(Co)+
5. Rut(Co)+z[RuC1z(COD)l, 1
．． [RuC1z(Co)3]z, Ru0z, Ru(a
cac)sRuClz(Co)z(PPhs)z, Ru
CIz(Co)3(PPh*).

RuCIz(Co): +(P(OPh)3), Ru(C
o) 4(PPhx) etc. are more preferred.

The amount of the catalyst used in the present invention varies depending on the reaction conditions, etc., but is usually about 10-'-10-' mol per 1 mol of the substrate.

In the present invention, a suitable solvent is present.

Examples of the solvent used in the present invention include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isoamyl alcohol, and t-amyl alcohol;
Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, etc. Glyme-based medium, tetrahydrofuran, ■, 4
- Ether solvents such as dioxane and anisole; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and the like. Among these, methanol,
Ethanol, isopropyl alcohol, n-butyl alcohol, diethylene glycol dimethyl ether,
Triethylene glycol dimethyl ether and ethylene glycol monoethyl ether acetate are preferred.

Further, in the present invention, when a homogeneous catalyst consisting of a rhodium compound or ruthenium compound and a solvent is used, the catalytic activity is improved compared to the conventional method, and further, the presence of an amine compound in the reaction system significantly improves the catalytic activity.

Further, in the present invention, by using a homogeneous catalyst consisting of a ruthenium compound and a solvent, and by allowing an amine compound to be present and a copper compound to coexist, the catalytic activity is further significantly improved.

The amine compound used in the present invention is one type of amine compound selected from amines represented by the form (1), NR'R"R' (1) pyridines, imidazoles, and chelating diamines. be.

-C The amines represented by formula (1), in the formula, R1゜R2
R3 represents hydrogen, an alkyl group, or an aryl group, and R1, RZ, and Ral are never hydrogen at the same time. Also R1. Any one of R2, R3 is hydrogen, and R1, R1, R3 together form a ring, for example, (CI, -9 to (CL) a)
, (CI(2) 5(CI(2)!-NH-(C
H2)2-, etc. are mentioned.

Pyridines are compounds that have a pyridine skeleton, and imidazoles are compounds that have an imidazole skeleton.

In addition, chelating diamines are two nitrogen atoms with 22'
chelating amines at positions 1, 1, 2 (including 2, 3, 9, 10), 1.3, 1.4, 1.5, 1.8, and 1.10. It refers to

Examples of the amine compounds used in the present invention include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, dimethylamine, diethylamine, diisopropylamine, di-n-propylamine, di-n-butyl amine, methylamine, ethylamine, isopropyl Amines, amines having an alkyl group having 1 to 5 carbon atoms such as n-propylamine, n-butylamine, and ethyldiisopropylamine, aniline, 1-aminoanthraquinone, 2-aminoanthraquinone, N-methylaniline, N-ethylaniline, etc. Amines having an aryl group, cyclic amines such as pyrrole, pyrrolidine, piperidine, piperazine, pyridine, α-picoline, β-picoline, T-picoline, 4,4-dimethylaminopyridine, 2-cyanopyridine, 3-cyano Pyridines such as pyridine, 4-cyanopyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine,
Imidazole such as imidazole, N-methylimidazole, N-ethylimidazole, henzimidazole, 2-methylhenzimidazole, N-methylhenzimidazole, 9.10-diaminophenanthrene, 1.10
-phenanthroline, 3478-tetramethyl-110
-phenanthroline, 3.4.5.6.7゜8-hexamethyl-110-phenanthroline, 0-phenylenediamine, N,N,N,N-tramethyl-〇-phenylenediamine, 2,3 naphthalenediamine, 1,8- Examples include chelating diamines such as naphthalene diamine, 1,5-naphthalene diamine, 1,8-bis(dimethylamino)naphthalene, and 2,3-bis(dimethylamino)naphthalene. Among these, the amine compounds used in the present invention include triethylamine, tri-n-propylamine, diethylamine, diisopropylamine, 1-aminoanthraquinone, piperidine, 4-anopyridine,
-methylhenzimidazole, 1,8-bis(dimethylamino)naphthalene, N,N,N",N-tetramethyl-〇-phenylenediamine are preferred.

The above amine compound is usually 0.0% per atomic weight of the catalyst metal.
01 to 500 times the molar amount, more preferably o, oi
~300 mil 300 times mole.

The copper compound used in the present invention refers to a monovalent or divalent copper compound, and examples thereof include compounds such as oxides, halides, hydroxides, carboxylates, sulfates, nitrates, and carbonates. More specifically, cuprous oxide, cupric oxide, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, water. Copper oxide, copper acetate, copper oxalate,
Examples include copper formate, copper naphthenate, copper stearate, copper sulfate, copper nitrate, and copper carbonate.

Among these, cupric oxide, copper carbonate, cupric bromide, and copper acetate are preferred.

The above-mentioned copper compound is usually used in an amount of 0.01 to 500 times the copper atomic weight per catalytic metal atomic weight, and more preferably 0.01 to 500 times the mol.
．． 01 to 100 times the molar amount.

The reaction temperature of the present invention is usually 0 to 250°C, preferably 20 to 200°C.

The pressure of CO used in the present invention is not particularly limited, but is usually 1
The pressure may be -100 atmospheres or more.

[Effects of the Invention] As detailed above, the present invention can be applied under Co/)120 conditions.
It has a very significant catalytic activity in the liquid phase and reduces only the nitro group with very high selectivity, making it possible to obtain the desired aminoanthraquinone in high yield. Furthermore, since the product aminoanthraquinone has low solubility and precipitates as crystals after the reaction, the catalyst and aminoanthraquinone can be easily separated by filtration, and the catalyst can be easily recycled.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 Ru, (Co)+z (0,005 mmo1) was placed in a stainless steel magnetically stirred autoclave with an internal volume of 110 cc.
, Metatsuru 15d, water 5, and 3.0 g (10,2101) of 1-nitroanthraquinone (manufactured by Tokyo Kasei ■, 86.2% purity, 13.8% anthraquinone), CO pressure 20 kg/c + fl, 150 The mixture was stirred at °C and the reaction was carried out for 2 hours.

The reaction product was quantitatively analyzed by gas chromatography and liquid chromatography, and its identification was performed by comparison of retention times of chromatograms, elemental analysis, and GC-MS.

Further, the following total turnover number (TN) was used as an index indicating the activity of the catalyst.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (4,8mmo+), and no other by-products were present. The nitro group selectivity was 100%. Also, T
N was 969.

Note that the following examples and comparative examples were also conducted using the same analytical method.

Examples 2 to 40 Example 1 except that the solvent and amine compound shown in Table 1 were used.
The reaction was carried out under the same conditions.

As a result of analysis, the reaction product was only 1-aminoanthraquinone, and no other by-products were found. Further, the nitro group selectivity of each Example was 100%.

The results are shown in Table 1.

Table continued 1) Molar ratio: Amount of amine compound - 1)/1 Mosquito ■Kintanjo Fr
(■-atm) Examples 41 to 43 Rha (Co) + b (0,005m
The reaction was carried out under the same conditions as in Example 1, except that the solvent shown in Table 2 was used.

As a result of analysis, the reaction product was only 1-aminoanthraquinone, and no other by-products were present.

Further, the nitro group selectivity of each Example was 100%.

The results are shown in Table 2.

Table 2 The nitro group selectivity of each example was 100%.

The results are shown in Table 3.

Table 3 Examples 44 to 48 The reaction was carried out under the same conditions as in Example 42 except that the amine compounds shown in Table 3 were added.

As a result of analysis, the reaction product was only l-aminoanthraquinone, and no other by-products were present. Further, Example 49 Rh4(Co)+z (0,005 mmol) as a catalyst
using 3.4.7.8-tetramethyl1.10-phenanthroline (0,005 mmol) as the amine compound.
) was added thereto, and the reaction was carried out in ethanol under the same conditions as in Example 1.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (1.72 mmol), and no other by-products were found. The nitro group selectivity was 100%. Moreover, TN was 345.

Example 50 4,4-dimethylaminopyridine (
1.5 mmol) was added thereto, and the reaction was carried out in 2-methoxyethanol under the same conditions as in Example 49.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (1.68 mmol), and no other by-products were found. The nitro group selectivity was 100%.

Moreover, TN was 337.

Examples 51 to 55 1.5 mmo of triethylamine as an amine compound
The reaction was carried out under the same conditions as in Example 1, except that the reaction temperature and Co pressure shown in Table 4 were used. However, in Examples 53 to 55, the reaction time was 90 minutes.

As a result of analysis, the reaction product was only l-aminoanthraquinone, and no other by-products were found. Further, the nitro group selectivity of each Example was 100%.

The results are shown in Table 4.

Example 56.57 The reaction was carried out under the same conditions as in Example 1, except that 0.002 mmol of the catalyst and 1.5 mmol of triethylamine as an amine compound were added, and the solvent shown in Table 5 was used at 18.0°C. .

As a result of analysis, the reaction product was only 1-aminoanthraquinone, and no other by-products were found. Further, the nitro group selectivity of each Example was 100%.

The results are shown in Table 5.

Table 4 Table 5 Example 58 The reaction was carried out under the same conditions as in Example 1 except that the catalyst Ru1(Co)+z was 0.01 mmol, 5 mmol of triethylamine was added, and ethanol was used as the solvent.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (10.2 mmol), and no other by-products were found. The nitro group selectivity was 100%.

Moreover, TN was 1020.

Example 59 The reaction was carried out under the same conditions as Example 28 except that the reaction time was 5 hours.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (10.2 mmol), and no other by-products were found. The nitro group selectivity was 100%.

Moreover, TN was 2040.

Furthermore, as a result of analyzing the gas after the reaction, CO□30.2
mmol, Hz 0.02 mmol, and the production of H2 was very small.

Example 60 The reaction was carried out under the same conditions as in Example 14, except that the reaction time was 5 hours, the catalyst was 0.0 In+mol, and the pyrrolidine was 0.045 mmol.

As a result of analysis, the reaction product was only 1-aminoanthraquinone (10.2 mmol), and no other by-products were found. The nitro group selectivity was 100%.

Moreover, TN was 1020.

Furthermore, as a result of analyzing the gas after the reaction, C0ff134
, 2mmol, Hz 0.08n+mol,
The production of H2 was negligible.

Example 61 Ru3(Co)+z (0.01 mmol), methanol (15 m), water (5 Id), triethylamine (1°5 mmol), and nitroanthraquinone (2 g) were placed in a stainless steel magnetic stirring autoclave with an internal volume of 110 cc.
was added and stirred at 150°C under a CO pressure of 20 kg/cJ to carry out a reaction for 6 hours.

Nitroanthraquinone is mononitroanthraquinone 7
4.9%, dinitroanthraquinone 23.5%, and anthraquinone 1.6%.

As a result of the analysis, all the nitro groups of nitroanthraquinone were reduced in the reaction products, and the corresponding I-aminoanthraquinone, 2-aminoanthraquinone, 1,5-diaminoanthraquinone, 1,8-diaminoanthraquinone, etc. were found.

The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 99% or more.

Example 62 Example 61 except that the solvent was isopropyl alcohol
The reaction was carried out under the same conditions.

As a result of analysis, the reaction product was the corresponding aminoanthraquinone in which all the nitro groups of nitroanthraquinone were reduced.

The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 99% or more.

Example 63 Diethylene glycol dimethyl ether was used as a solvent, and piperidine (0.09 mm) was used as an amine compound.

The reaction was carried out under the same conditions as in Example 61 except that 1) was added.

As a result of analysis, 1-nitroanthraquinone was reduced by 98%, and the reaction product was I-aminoanthraquinone. The nitro groups of all other nitroanthraquinones were reduced and the reaction product was the corresponding aminoanthraquinone.

The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 98% or more.

Example 64 An autoclave with an internal volume of 260 mP was equipped with a thermometer, a tabine blade stirrer, and a cooling pipe, and a gas flow reaction device was used in which carbon monoxide could flow from the lower part of the autoclave.

Ru (acac) + (0,10 mmo) in the autoclave
l), ethylene glycol monoethyl ether acetate (60 ml), water (23 d), aminoanthraquinone (0.11 g) and nitroanthraquinone (log)
and while maintaining the CO pressure of 20 kg/cT1,
The reaction was carried out for 3 hours by flowing at 0 m/min and stirring at 800 rpm at 170°C.

Nitroanthraquinone is mononitroanthraquinone 7
4.9% dinitroanthraquinone, 23.5% dinitroanthraquinone, and 1.6% anthraquinone.The aminoanthraquinone used was 74.9% monoaminoanthraquinone, 23.5% diaminoanthraquinone, and 1.6% anthraquinone.
A material consisting of was used.

As a result of the analysis, all of the nitro groups of nitroanthraquinone in the reaction product were reduced, and corresponding 1-aminoanthraquinone, 2-aminoanthraquinone, 1.5-diaminoanthraquinone, 1.8-diaminoanthraquinone, etc. were produced. The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 99.9% or more.

Example 65 Ru y instead of Ru (acac) * as catalyst
Aminoanthraquinone (88 mg) with the composition used in Example 64 using (CO) 1z (0.04 mmol)
The reaction was carried out for 2 hours in the same manner as in Example 64, except that n-butyl alcohol was used as the solvent.

As a result of the analysis, all the nitro groups of nitroanthraquinone were reduced in the reaction product, and corresponding niaminoanthraquinone, 2-aminoanthraquinone, 1.5-diaminoanthraquinone, 1.8-diaminoanthraquinone, etc. were produced. The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 86%.

Example 66 A reaction was carried out in the same manner as in Example 65 except that ethylene glycol monoethyl ether acetate was used instead of n-butyl alcohol as the solvent.

As a result of the analysis, all of the nitro groups of nitroanthraquinone in the reaction product were reduced, and corresponding l-aminoanthraquinone, 2-aminoanthraquinone, 15-diaminoanthraquinone, 1,8-diaminoanthraquinone, etc. were produced. The nitro group selectivity was 100%, and the yield of aminoanthraquinone was 90%.

Examples 67 to 70 [RuCIz (COD)] (0.1 mmol, manufactured by Kanto Kagaku ■) or Ru0z (0.1 mmol) was added with the additives shown in Table 6, and the same catalyst system was used. The reaction was carried out under the same conditions as in Example 66 for 3 hours.

As a result of the analysis, all of the nitro groups of nitroanthraquinone in the reaction product were reduced, and the corresponding 1-aminoanthraquinone, 2-aminoanthraquinone, 5-diaminoanthraquinone, 1,8-diaminoanthraquinone, etc. were produced. The nitro group selectivity was 100%.

The results are shown in Table 6.

Note that TN per nitro group is used as an indicator of catalytic activity.
was used.

Examples 71 to 74 In a stainless steel magnetic stirring autoclave with an internal volume of 111)-, R++5(CO)+z(0,005mmo+),
Ethylene glycol monoethyl ether acetate (1
5mQ), water (5d), triethylamine (1.5mm
ol) and nitroanthraquinone (2 g), Table 7
Add the copper compound shown in , CO pressure is 20kg/c! ,
The mixture was stirred at 150°C and the reaction was carried out for 2 hours.

The same nitroanthraquinone used in Example 64 was used.

In addition, the total turnover number as an index indicating the activity of the catalyst was used here as per nitro group.

As a result of analysis, the reaction product was aminoanthraquinone, and there were no by-products. The nitro group selectivity was 100%.

The results are shown in Table 7.

Table 7 Example 75 Using Rut(CO) +z (0,003 mmol) and nitroanthraquinone (3 g), reaction temperature 180'C
, The reaction was carried out under the same conditions as in Example 72 except that the CO pressure was 50 kg/cd.

As a result of the analysis, the reaction product showed that all the nitro groups of nitroanthraquinone were reduced, and the corresponding 1-aminoanthraquinone, 2-aminoanthraquinone, 1.5-diaminoanthraquinone, 1.8-diaminoanthraquinone, etc. were produced, and by-products There was no. Nitro group selectivity is 100%
Met. Moreover, TN was 4932.

Procedural amendment (voluntary) November 27, 1990 Display of the case 1990 Patent Application No. 222770 Name of the invention Person making an amendment to the manufacturing method of aminoanthraquinone Relationship to the case Patent applicant address Kitahama, Chuo-ku, Osaka 4-5-33 Name (
209) Sumitomo Chemical Co., Ltd. Representative Hideo Mori

Claims (4)

[Claims] (1) A method for producing aminoanthraquinone, which comprises reacting nitroanthraquinone with carbon monoxide and water in a liquid phase using a homogeneous catalyst comprising a rhodium compound or ruthenium compound and a solvent. (2) The method for producing aminoanthraquinone according to claim (1), wherein an amine compound is present in the catalyst according to claim (1). (3) Amines whose amine compound is represented by the general formula (I), NR^1R^2R^3(I) (wherein R^1, R^2, and R^3 are hydrogen, an alkyl group, or an aryl group, respectively. Represents a group, R^1, R^2, R^3
cannot be hydrogen at the same time. Also R^1, R^2,
R^3 may also be taken together to form a ring. ) The method for producing aminoanthraquinone according to claim (2), wherein the amine compound is at least one kind of amine compound selected from pyridines, imidazoles, and chelating diamines. (4) Aminoanthraquinone characterized by reacting nitroanthraquinone with carbon monoxide and water in a liquid phase using a homogeneous catalyst consisting of a ruthenium compound and a solvent and in the presence of an amine compound and a copper compound. manufacturing method.