Process for preparing 1,5-diaminonaphthalene derivative

Details Process for preparing 1,5-diaminonaphthalene derivative Process for preparing 1,5-diaminonaphthalene derivative

2003-01-02

2004-05-18

Davis, Brian (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

Reexamination Certificate

active

06737548

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process for preparing a 1,5-diaminonaphthalene derivative. In particular, it relates to a process for preparing a 1,5-diaminonaphthalene derivative using a 5-nitro-1-tetralone derivative as starting material. A 1,5-diaminonaphthalene derivative prepared according to the process of this invention is useful as a material for a variety of synthetic resins. For example, a 1,5-diaminonaphthalene derivative may be reacted with phosgene to form a diisocyanate, which may be then converted into a polyurethane resin, a dicarboxylic acid or its derivative to provide a polyamide resin.
BACKGROUND OF THE INVENTION
Conventionally, a 1,5-diaminonaphthalene derivative has been prepared by nitrating naphthalene to produce a dinitronaphthalene and then reducing the nitro groups into amino groups. Dinitration of naphthalene, however, produces a 1,8-dinitro derivative in a large amount in addition to the desired 1,5-dinitro derivative. For example, in nitration of 1-nitronaphthalene in a chlorine-containing organic solvent as described in Japanese Laid-open Patent Publication No. 51-070757, 1,5-dinitronaphthalene is produced in an yield of 30% while 1,8-dinitronaphthalene in an yield of 65%. That is, the 1,8-dinitro derivative is formed in a two-fold or more amount of the 1,5-dinitro derivative. 1,8-Dinitronaphthalene may be readily reduced into 1,8-diaminonaphthalene, which may be, for example, used as a material for a dye. However, when a demand for 1,8-diaminonaphthalene is reduced, production of 1,5-dinitronaphthalene is reduced, making 1,5-diaminonaphthalene less available.
In the light of such status, there have been attempts for increasing an yield of the 1,5-derivative in nitration of naphthalene. For example, WO 99-12887 has described that using Nafion® as an acid, 1-nitronaphthalene is nitrated with nitric acid to give 1,5- and 1,8-dinitronaphthalenes in yields of 34.1% and 38.0%, respectively. Thus, the proportion of the 1,5-dinitro derivative may be improved, but the 1,8-derivative is still formed in a large amount.
As described above, the current preparation procedure produces the 1,8-dinitro derivative in a large amount in addition to the 1,5-dinitro derivative. Thus, there has been needed to provide a process for selectively producing a 1,5-diaminonaphthalene derivative without forming isomers.
Besides the process involving dinitration of naphthalene and reduction of the nitro groups, many alternative processes have been suggested; for example, amination of 1,5-dihydroxynaphthalene as a starting material (U.S. Pat. No. 5,113,025, Japanese Laid-open Patent Publication No. 59-29061), amination of a 5-halogeno-1-aminonaphthalene or 1,5-dihalogenonaphthalene (Japanese Laid-open Patent Publication No. 7-278066, U.S. Pat. No. 3,787,496) and amination of sodium 1,5-naphthalenedisulfonate (Nihon Kagakukai Shi, 522 (1974)). However, a cumene process for preparing 1,5-dihydroxynaphthalene tends to cause rearrangement of a isopropyl group in 1,5-diisopropylnaphthalene as a starting material to the &bgr;-position due to steric hindrance, leading to formation of isomers as is in the process involving dinitration and reduction. It is, therefore, not a selective method. Halogenation or sulfonation of naphthalene is also less selective.
SUMMARY OF THE INVENTION
We have intensely investigated for providing a process for selectively preparing a 1,5-diaminonaphthalene derivative without forming isomers, and have found a process for preparing a 1,5-diaminonaphthalene derivative using a 5-nitro-1-tetralone derivative as an intermediate, achieving this invention.
Specifically, this invention comprises the embodiments described in the following [1] to [7].
[1] A process for preparing a 1,5-diaminonaphthalene derivative comprising:
(i) the first step comprising reacting an ortho-alkylnitrobenzene represented by formula (1):
wherein R
1
to R
4
, which may be the same or different, represent hydrogen, alkyl having 1 to 4 carbon atoms, aromatic hydrocarbon having 6 to 12 carbon atoms, or halogen; and R
5
represents hydrogen, with a vinyl compound represented by formula (2):
wherein R
6
and R
7
, which may be the same or different, represent hydrogen, alkyl having 1 to 4 carbon atoms, or halogen; and X represents an electron withdrawing group, provided that R
6
and R
7
are mutually cis- or trans-configured, in the presence of a base, to produce an aromatic nitro compound represented by formula (3):
wherein R
1
to R
7
are as defined in formulas (1) and (2); and X represents an electron withdrawing group, which may be the same as or different from X as defined in formula (2);
(ii) the second step of cyclizing the aromatic nitro compound represented by formula (3) to produce a 5-nitro-1-tetralone derivative represented by formula (4):
wherein R
1
to R
4
and R
6
to R
7
are as defined in formulas (1) and (2); and
(iii) the third step comprising reacting the 5-nitro-1-tetralone derivative represented by formula (4) with an amine to provide an intermediate, which is then reduced and aromatized to produce the 1,5-diaminonaphthalene derivative represented by formula (5):
wherein R
1
to R
4
and R
6
to R
7
are as defined in formulas (1) and (2).
[2] The process as described in [1], wherein X in formula (2) is one selected from the group consisting of CN and CO
2
R
8
where R
8
represents alkyl having 1 to 7 carbon atoms, cycloalkyl, aromatic hydrocarbon having 6 to 12 carbon atoms or aralkyl.
[3] The process as described in [1], wherein X in formula (3) is one selected from the group consisting of CONH
2
, CN, CO
2
H and CO
2
R
8
where R
8
represents alkyl having 1 to 7 carbon atoms, cycloalkyl, aromatic hydrocarbon having 6 to 12 carbon atoms or aralkyl.
[4] The process as described in [1] or [2], wherein the reaction of the ortho-alkylnitrobenzene represented by formula (1) with the vinyl compound represented by formula (2) in the first step is conducted in the presence of at least one selected from the group consisting of a solvent capable of dissolving at least part of the base and a catalyst capable of solubilizing the base.
[5] The process as described in [4], wherein the solvent capable of dissolving at least part of the base is a circular urea derivative.
[6] The process as described in any of [1] to [5], wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):
wherein R
1
to R
4
and R
6
to R
7
are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):
wherein R
1
to R
4
and R
6
to R
7
arc as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).
[7] The process as described in any of [1] to [5], wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):
wherein R
1
to R
4
and R
6
to R
7
are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).
The above process wherein an ortho-alkylnitrobenzene derivative and a vinyl compound are used as starting materials to give a 5-nitro-1-tetralone derivative, from which a corresponding 1,5-diaminonaphthalene derivative is prepared, allows the 1,5-diaminonaphthalene derivative to be selectively prepared without forming isomers.
DETAILED DESCRIPTION OF THE INVENTION
First, there will be described the first step in the process according to th

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