Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2002-08-08
2003-11-04
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S041000, C556S112000, C556S117000, C427S593000
Reexamination Certificate
active
06642401
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a &bgr;-diketonatocopper(I) complex useful in forming a thin copper film by metal-organic vapor deposition (hereinafter abbreviated as MOCVD) method and a process for producing the same.
BACKGROUND ART
Conventionally, as a raw material for forming a thin copper film by MOCVD method, is well known &bgr;-diketonatocopper(I) complex comprising (vinyltrimethylsilane) (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) copper(I) of formula (&agr;)
disclosed in Japanese Patent Laid-open No. Hei 5-59551.
However, vinyltrimethylsilane is used as a ligand for the &bgr;-diketonatocopper(I) complex of the formula (&agr;). Conventionally, &bgr;-diketonatocopper(I) complex in which an allene compound is used as a ligand has not been known.
DISCLOSURE OF INVENTION
The present inventors research hard to find out novel &bgr;-diketonatocopper(I) complex in which an allene compound is used as a ligand from the above-mentioned viewpoint, and come to obtain &bgr;-diketonatocopper(I) complexes of formula (2) described below in which an allene compound of formula (1) described below is used as a ligand.
That is, the present invention relates to a &bgr;-diketonatocopper(I) complex which contains as a ligand (L) an allene compound of formula (1)
wherein R
1
, R
2
, R
3
and R
4
may be the same or different and each represents hydrogen, C
1-4
alkyl or (R
5
)
3
Si—, or R
1
and R
2
, together with the carbon atom bonding them, may form 3- to 6-member ring, or R
2
and R
3
, together with the allene bond group bonding them, may form 8- to 10-member ring, R
5
s may be the same or different and independently of one another represent linear or branched C
1-4
alkyl, and which is represented by formula (2)
wherein, R
6
and R
7
may be the same or different and each represents linear or branched C
1-4
alkyl, C
1-4
alkoxy, or linear or branched C
1-4
fluoroalkyl, R
8
represents hydrogen or fluorine, and L represents the allene compound of formula (1).
Then, the present invention will be concretely explained.
The following is exemplified for each of the substituents in the chemical structural formula of allene compounds represented by formula (1) that is the ligand in the &bgr;-diketonatocopper(I) complexes of formula (2).
The substituents R
1
, R
2
, R
3
and R
4
include, for example H, Me, Et, n-Pr, n-Bu, i-Pr, i-Bu, s-Bu, t-Bu, Me
3
Si, Et
3
Si, n-Pr
3
Si, n-Bu
3
Si, i-Pr
3
Si, i-Bu
3
Si, s-Bu
3
Si, t-Bu
3
Si, Me
2
(Et)Si, Me
2
(n-Pr)Si, Me
2
(n-Bu)Si, Me
2
(i-Pr)Si, Me
2
(i-Bu)Si, Me
2
(s-Bu)Si, Me
2
(t-Bu)Si, Et
2
(Me)Si, Et
2
(n-Pr)Si, Et
2
(n-Bu)Si, Et
2
(i-Pr)Si, Et
2
(i-Bu)Si, Et
2
(s-Bu)Si, Et
2
(t-Bu)Si, n-Pr
2
(Me)Si, n-Pr
2
(Et)Si, n-Pr
2
(i-Pr)Si, n-Pr
2
(n-Bu)Si, n-Pr
2
(s-Bu)Si, n-Pr
2
(t-Bu)Si, n-Bu
2
(Me)Si, n-Bu
2
(Et)Si, n-Bu
2
(n-Pr)Si, n-Bu
2
(i-Pr)Si, n-Bu
2
(i-Bu)Si, n-Bu
2
(s-Bu)Si, n-Bu
2
(t-Bu)Si, i-Pr
2
(Me)Si, i-Pr
2
(Et)Si, i-Pr
2
(n-Pr)Si, i-Pr
2
(n-Bu)Si, i-Pr
2
(s-Bu)Si, i-Pr
2
(t-Bu)Si, i-Bu
2
(Me)Si, i-Bu
2
(Et)Si, i-Bu
2
(n-Pr)Si, i-Bu
2
(n-Bu)Si, i-Bu
2
(i-Pr)Si, i-Bu
2
(s-Bu)Si, i-Bu
2
(t-Bu)Si, s-Bu
2
(Me)Si, s-Bu
2
(Et)Si, s-Bu
2
(n-Pr)Si, s-Bu
2
(n-Bu)Si, s-Bu
2
(i-Pr)Si, s-Bu
2
(i-Bu)Si, s-Bu
2
(t-Bu)Si, t-Bu
2
(Me)Si, t-Bu
2
(Et)Si, t-Bu
2
(n-Pr)Si, t-Bu
2
(n-Bu)Si, t-Bu
2
(i-Pr)Si, t-Bu
2
(i-Bu)Si or t-Bu
2
(s-Bu)Si.
When R
1
and R
2
, together with the carbon atom bonding them, form 3- to 6-member ring, the ring includes cyclopropane ring, cyclobutane ring, cyclopentane ring or cyclohexane ring.
When R
2
and R
3
, together with the allene bond group bonding them, form 8- to 10-member ring, the ring includes cyclooctane ring, cyclononane ring or cyclodecane ring.
The following is exemplified for each of the substituents in the chemical structural formula of the &bgr;-diketonatocopper(I) complexes of formula (2).
The substituents R
6
and R
7
include, for example, CF
3
, C
2
F
5
, n-C
3
F
7
, i-C
3
F
7
, n-C
4
F
9
, Me, Et, n-Pr, n-Bu, i-Pr, i-Bu, s-Bu, t-Bu, MeO, EtO, n-PrO, n-BuO, i-PrO, i-BuO, s-BuO or t-BuO. In addition, the substituent R
8
includes, for example H or F.
The present invention also relates to a process for producing a &bgr;-diketonatocopper(I) complex represented by formula (2)
wherein, R
6
and R
7
may be the same or different and each represents linear or branched C
1-4
alkyl, C
1-4
alkoxy, or linear or branched C
1-4
fluoroalkyl, R
8
represents hydrogen or fluorine, and L represents the allene compound of formula (1), characterized in that the process comprises reacting an allene compound of formula (1)
wherein R
1
, R
2
, R
3
and R
4
may be the same or different and each represents hydrogen, C
1-4
alkyl or (R
5
)
3
Si—, or R
1
and R
2
, together with the carbon atom bonding them, may form 3- to 6-member ring, or R
2
and R
3
, together with the allene bond group bonding them, may form 8- to 10-member ring, R
5
s may be the same or different and independently of one another represent linear or branched C
1-4
alkyl, with an enol compound of formula (3)
wherein R
9
and R
10
may be the same or different and each represents linear or branched C
1-4
alkyl, C
1-4
alkoxy, or linear or branched C
1-4
fluoroalkyl, R
11
represents hydrogen or fluorine in the presence of a copper(I) compound.
Next, the process for producing a &bgr;-diketonatocopper(I) complex according to the present invention will be explained in more detail on the basis of reaction formulae (A) and (B).
in formula (1) in reaction formula (A), R
1
, R
2
, R
3
and R
4
may be the same or different and each represents hydrogen, C
1-4
alkyl or (R
5
)
3
Si—, or R
1
and R
2
, together with the carbon atom bonding them, may form 3- to 6-member ring, or R
2
and R
3
, together with the allene bond group bonding them, may form 8- to 10-member ring, R
5
s may be the same or different and independently of one another represent linear or branched C
1-4
alkyl, in formula (3) or (4), R
9
and R
10
may be the same or different and each represents linear or branched C
1-4
alkyl, C
1-4
alkoxy, or linear or branched C
1-4
fluoroalkyl, R
11
represents hydrogen or fluorine, in formula (2), R
6
and R
7
may be the same or different and each represents linear or branched C
1-4
alkyl, C
1-4
alkoxy, or linear or branched C
1-4
fluoroalkyl, R
8
represents hydrogen or fluorine, and L represents the allene compound of formula (1).
In the reaction represented by reaction formula (A), a &bgr;-diketonatocopper(I) complex in which an allene compound is coordinated can be synthesized by reacting an allene compound of formula (1) with an enol compound of formula (3) or a carbonyl compound of formula (4) (the compound of formula (4) is a tautomer of the compound of formula (3)) together with a copper(I) compound (CuX) of formula (5) optionally in the presence of a base (for example, inorganic base, such as sodium hydride, potassium hydride, sodium amide, potassium tertiary butoxide, potassium carbonate or the like).
The copper(I) compound includes, for example, Cu
2
O, CuF, CuCl, CuBr, Cul, CuOAc, CuCN, CuSCN, CuOTf and so on.
The enol compound of formula (3) is a tautomer of the carbonyl compound of formula (4) as indicated in reaction formula (B).
The molar ratio of the allene compound to the enol compound may be arbitrarily set. However, it is preferable that the enol compound and allene compound are mixed in an amount equimolar or close thereto. For example, the molar ratio of the enol compound to the allene compound may be 0.5 to 1.5.
The molar ratio of the allene compound to the copper(I) compound may be arbitrarily set. However, it is preferable that copper atoms in the copper(I) compound are equimolar with allene compound or that an excessive of the copper atoms is mixed with the allene compound. For example, the molar ratio of the copper atoms to the allene compound may be 0.5 to 3. The molar ratio of the base to the allene compound may be arbitrarily set. However, it is preferable that the base is equimolar with the allene compound or that an excessive of the base is mixed with the allene compound. For example, the molar ra
Kawamura Yasuo
Musashi Hideki
Watanabe Hisayuki
Nazario-Gonzalez Porfirio
Nissan Chemical Industries Ltd.
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