Method for producing mono-organoboranes or di-organoboranes

Details Method for producing mono-organoboranes or di-organoboranes Method for producing mono-organoboranes or di-organoboranes

2001-06-14

2003-07-29

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Boron acids or salts thereof

C564S009000, C558S298000

Reexamination Certificate

active

06600066

ABSTRACT:

The present invention relates to a novel process for preparing perhalogenated monoorganoboranes or diorganoboranes, which makes it possible to obtain these compounds under conditions which can readily be implemented in industry.
Various methods of preparing diorganohydroxyboranes are described in the prior art. Thus, Davidson et al. describe the preparation of diorganohydroxyboranes from dioxyorganoboranes using Grignard compounds (J. M. Davidson et al., French Soc, 1960, 191). The preparation of diorganohydroxyboranes from Lewis base-diorganooxyboranes is likewise known. For this purpose, diarylhydroxyborane compounds with 2-aminoethanol are prepared as salts with the aid of aqueous mineral acids. Acid hydrolysis gives the desired diorganohydroxyboranes (R. L. Letsinger, I. Skoog, J. Am. Chem. Soc., 77, 1955, 2491).
Thus, for example, reaction of trimethoxyboroxins with 2 equivalents of phenylmagnesium bromide and subsequently with ethanolamine gives (2-aminoethoxy)bis(phenyl)borane from which the corresponding diphenylhydroxyborane is synthesized as described (T. P. Povlock, W. T. Lippincott, J. Am. Chem. Soc., 80, 1958, 5409). Triorganooxyboranes react with 2 equivalents of Grignard compound and subsequent hydrolysis to give the desired diorganbhydroxyboranes (R. M. Washburn, F. A. Billig, M. Bloom, C. F. Albright, E. Levens, Advan. Chem. Ser., 32, 208, 1961).
Partially halogenated or perhalogenated diphenylhydroxyboranes have hitherto not been obtainable via these routes. Thus, di(pentafluorophenyl)hydroxyborane can be prepared by hydrolysis of di(pentafluorophenyl)chloroborane in acetone (R. D. Chambers, T. Chivers, J. Chem. Soc., 1965, 3933). The preparation of di(pentafluorophenyl)chloroborane is carried out by reacting dimethylbis(pentafluorophenyl)tin with boron trichloride under superatmospheric pressure in a bomb tube and can therefore not be employed in this form in industry. In addition, the yields of di(pentafluorophenyl)chloroborane, which is used as precursor for preparing di(pentafluorophenyl)hydroxyborane, obtained in this process are extremely low at only 36% (R. D. Chambers, T. Chivers, J. Chem. Soc., 1965, 3933). The synthesis of di(pentafluorophenyl)hydroxyborane from di(pentafluorphenyl)chloroborane in acetone using stoichiometric amounts of water is likewise unsatisfactory, giving a yield of only 49%.
Organoboron compounds are effective cocatalysts in the polymerization of olefins using metallocenes (M. Bochmann, J. Chem. Soc., Dalton Trans, 1996, 255-270). Partially halogenated or perhalogenated diorganohydroxyboranes in particular serve as precursors for preparing appropriate cocatalysts.
For this reason, there is a great need for a simple process for preparing the compounds mentioned at the outset, which process can, firstly, be carried out on an industrial scale while avoiding the formation of stannane compounds in the preparation and, secondly, provides the target compound in good yields.
We have now surprisingly found that organohaloarylborane compounds can be converted into the corresponding diorganohydroxy compounds in virtually quantitative yield by hydrolysis at elevated temperatures.
The present invention provides a process for preparing compounds of the formula (I)
(
C
6
R
1
5
)
1+1
M
(
XR
9
p
)
2−1
  (I)
where
R
1
are identical or different and are each, independently of one another, a hydrogen atom, a halogen atom or a C
1-C
20
group such as C
1
-C
20
-alkyl, C
6
-C
14
-aryl, C
1
-C
10
-alkoxy, C
2
-C
10
-alkenyl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, C
6
-C
10
-aryloxy, C
1
-C
10
-haloalkyl, C
6
-C
10
-haloaryl, C
2
-C
10
-alkynyl or C
3
-C
20
-alkylsilyl,
M is an element of main group III of the Periodic Table of the Elements, preferably aluminum or boron, very particularly preferably boron,
X are identical or different and are each, independently of one another, an element of main group V or VI of the Periodic Table of the Elements, preferably oxygen or nitrogen,
R
9
is a hydrogen atom or a C
1
-C
20
group such as C
1
-C
20
-alkyl or C
6
-C
14
-aryl,
p is 1 or 2,
l is 0 or 1,
by reacting a compound of the formula (II)
(
C
6
R
1
5
)
1+n
M
1
R
2
2−n
  (II)
where
R
1
is as defined under formula (I),
M
1
is an element of main group III of the Periodic Table of the Elements, preferably aluminum or boron, very particularly preferably boron,
R
2
are identical or different and are each, independently of one another, a hydrogen atom, a halogen atom or a C
1
-C
20
group such as C
1
-C
20
-alkyl, C
6
-C
14
-aryl or C
6
-C
14
-haloaryl, particularly preferably a C
6
-C
8
-fluoroaryl group, very particularly preferably a perfluorinated phenyl ring and
n is an integer from 0 to 2
with a compound of the formula (III)
B
1
R
3
R
4
  (III)
where
R
3
,R
4
are identical or different and are each, independently of one another, a hydrogen atom, a halogen atom, a C
1
-C
20
group such as C
1
-C
20
-alkyl, C
6
-C
14
-aryl, C
1
-C
10
-alkoxy, C
2
-C
10
-alkenyl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, C
6
-C
10
-aryloxy, C
1
-C
10
-haloalkyl, C
6
-C
10
-haloaryl, C
2
-C
10
-alkynyl, C
3
-C
20
-alkylsilyl, an —OR
6
2
group, where R
6
is a C
1
-C
20
group such as C
1
-C
20
-alkyl or C
6
-C
14
-aryl, or one or more radicals R
3
, R
4
form an —NR
7
2
group, where R
7
is a hydrogen atom, a halogen atom or a C
1
-C
20
group such as C
1
-C
20
-alkyl or C
6
-C
14
-aryl,
B
1
is an element of main group V or VI of the Periodic Table of the Elements, preferably oxygen or nitrogen, particularly preferably oxygen,
or alternatively or additionally with an inorganic salt of the formula (IV),
Z
j
(
VY
h
)
i
*B
1
R
3
R
4
  (IV)
where
R
3
,R
4
are each a hydrogen atom,
B
1
is an element of main group V or VI of the Periodic Table of the Elements, preferably oxygen or nitrogen, particularly preferably oxygen,
Z can be an element of main group I, II, III or IV or an element of transition groups I-VIII, or a mixture of elements from these groups, or is (NH
4
),
V is an element of main group IV, V, VI or VII or an element of transition groups I-VIII,
Y is an element of main group IV, V, VI or VII or an element of transition groups I-VIII,
j, h, i are each a number in the range from 0 to 1000,
at a temperature above room temperature, to form the compound of the formula (I).
The product of the formula (I) formed can, if desired, be worked up further by appropriate means. This can be achieved, for example, by extraction of the compound (I) using aprotic, aliphatic and/or aromatic hydrocarbons, with any solid residues being able to be separated off.
After extraction, the extractant is separated off and, depending on the purity desired, further purification of the compound of the formula (I) can be carried out.
Preferred, nonlimiting examples of compounds of the formula (III) are water and/or alcohols such as methanol, ethanol, propanol or butanol, and also mixtures of these.
Preferred, nonlimiting examples of compounds of the formula (IV) are AlCl
3
*6H
2
O, Al(NO
3
)
3
*9H
2
O, Al
2
(SO
4
)
3
*18H
2
O, NH
4
Cr(SO
4
)
2
*12H
2
O, (NH
4
)
2
Fe(SO
4
)
3
*6H
2
O, (NH
4
)
2
Fe(SO
4
)
3
*12H
2
O, NH
4
MgPO
4
*6H
2
O, (NH
4
)
2
SO
3
*H
2
O, (NH
4
)W
7
O
24
*6H
2
O, BaBr
2
*2H
2
O, Ba(ClO
3
)
2
O, Ba(NO
2
)
2
*H
2
O, Cr(NO
3
)
3
*6H
2
O, Cr
2
(SO
4
)
3
*18H
2
O, Na
2
HPO
4
*12H
2
O, Fe(NO
3
)
3
*9H
2
O, FeSO
4
*7H
2
O, CdCl
2
*2.5H
2
O, KAl(SO
4
)
2
*12H
2
O, K
4
[Fe(CN)
6
]*3H
2
O, CuCl
2
*2H
2
O, Cu(NO
3
)
2
*3H
2
O, Mg(NO
3
)
2
*6H
2
O, MgSO
4
*7H
2
O, Na
2
SO
3
*7H
2
O, NiSO
4
*7H
2
O, and mixtures of these.
The process of the present invention makes it possible to obtain, in particular, the compounds bis(pentafluorophenyl)hydroxyborane, di(phenyl)hydroxyborane, di(o-tolyl)hydroxyborane, di(p-anisyl)hydroxyborane, di(nonafluorobiphenyl)hydroxyborane, di(trifluoromethyl)phenylhydroxyborane, di(p-biphenyl)hydroxyborane, di(p-chlorophenyl)hydroxyborane, di(p-fluoro-1-naphthyl)phenylhydroxyborane or pentafluorophenyldihydroxyborane in industrial quantities.
The way in which the process of the

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