Process for the preparation of organic solutions

Details Process for the preparation of organic solutions Process for the preparation of organic solutions

2002-12-16

2004-04-27

Shippen, Michael L. (Department: 1621)

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

Organic compounds

Oxygen containing

Reexamination Certificate

active

06727393

ABSTRACT:

FIELD OF THE INVENTION
The invention concerns a process for the preparation of organic solutions and in particular solutions containing a quaternary cation and an anion from a deprotonated hydroxy.
SUMMARY OF THE INVENTION
A process for the preparation of a solution of a quaternary cation and an anion from a deprotonated hydroxy aromatic in an organic solvent by means of a reactive extraction of a quaternary salt in the presence of an aqueous hydroxide solution, a hydroxy aromatic and an organic solvent is disclosed. Also disclosed is a process for the recycling of a quaternary salt phenolate solution from a reaction mixture.
BACKGROUND OF THE INVENTION
Salts of quaternary cations and anions from deprotonated hydroxy aromatics, particularly quaternary salt phenolate solutions, may be used in a variety of organic reactions as bases, catalysts or reaction components. Since such salts are not commercially available and their educts are relatively expensive, methods of synthesising these salts and of recovering them from reaction mixtures are required.
DE A 19858967 describes a process for preparing liquid formulations of tetrabutyl ammonium phenolate. Phenolic solutions of tetrabutyl ammonium bromide and sodium phenolate are combined, excess phenol is distilled off and sodium bromide removed by filtration.
The disadvantage of this process is firstly that phenol must be distilled off, requiring a considerable amount of energy, and secondly that the sodium bromide, which may occur as a very finely crystalline deposit, may possibly be difficult to isolate. It is therefore desirable to work out a simpler process that requires less equipment. A further object concerns the recovery of quaternary cation phenolate salts from reaction mixtures. The process should therefore also offer the possibility of reprocessing reaction mixtures in such a way that the quaternary cation phenolate solutions may be recycled.
In working on this object a very simple reactive extraction process was found, with which surprisingly an almost quantitative conversion with surprisingly high extraction yields of organic quaternary salt phenolate solutions are produced, even in a single-stage extraction, with no troublesome by-products.
The invention therefore provides a process for the preparation of organic solutions of salts (Q
n+
)
k
[(
−
O)
k
—R]
n
from a quaternary cation (Q
n+
) and a hydroxy aromatic (R
1
—(OH)
k
), characterised in that an aqueous solution of a hydroxide M
r+
(OH
−
)
r
, at least one quaternary salt (Q
n+
)
m
[Y
m−
]
n
, R
1
—(OH)
k
and at least one solvent that is not completely miscible with water are brought into intimate contact and the aqueous phase is then separated off from the organic phase containing (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
and optionally R
1
(OH)
k
and/or (Q
n+
)
m
[Y
m−
]
n
.
The invention also provides a process for the recovery of quaternary salts from reaction mixtures and their recycling as organic solutions of mixtures of salts (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
and (Q
n+
)
m
[Y
m−
]
n
. In the process a mixture that comprise
1. one or more quaternary salts (Q
n+
)
m
[Y
m−
]
n
2. a hydroxy aromatic R
1
—(OH)
k
and optionally
3. one or more organic solvents is reacted as follows:
a) an aqueous solution of a hydroxide M
r+
(OH
−
)
r
and an organic solution containing the quaternary salt (Q
n+
)
m
[Y
m−
]
n
are brought into intimate contact and the aqueous phase is then separated from the organic phase containing (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
and (Q
n+
)
m
[Y
m−
]
n
and/or R
1
—(OH)
k
.
b) The (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
contained in this organic solution along with the R
1
(OH)
k
and/or (Q
n+
)
m
[Y
m−
]
n
that are optionally present is returned to the reaction after optional additional reprocessing steps.
The present invention also provides a process for the preparation of organic solutions of salts (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
and (Q
n+
)
m
[Y(1)
m−
]
n
from a quaternary cation (Q
n+
) and a hydroxy aromatic (R
1
—(OH)
k
), characterised in that an aqueous solution of a hydroxide M
r+
(OH
−
)
r
having at least two different quaternary salts (Q
n+
)
m
[Y(1)
m−
]
n
and (Q
n+
)
p
[Y(2)
p−
]
n
and at least one solvent that is not completely miscible with water are brought into intimate contact and the aqueous phase is then separated from the organic phase containing (Q
n+
)
k
[(
−
O)
k
—R
1
]
n
and (Q
n+
)
m
[Y(1)
m−
]
n
. (Q
n+
)
m
[Y(1)
m−
]
n
and (Q
n+
)
p
[Y(2)
p−
]
n
are two different members of the large number of compounds defined by (Q
n+
)
m
[Y
m−
]
n
, where m and p are natural numbers which may be the same or different. m is preferably smaller than p. Halide (X
−
) and sulfate (SO
4
2−
) are a preferred combination of Y(1)
m−
and Y(2)
p−
, where bromide (Br
−
) and sulfate are particularly preferred.
The quaternary salts used in connection with the present invention are typically compounds having the formula (XR
o
+
)
n
, whereby X stands for an atom from group Va or VIa, o for a whole number between 0 and 4 and R mutually independently for C
6
to C
18
aryl, C
7
to C
18
aralkyl or C
1
to C
20
alkyl radicals, and n stands for a natural number.
These include ammonium, guanidinium, phosphonium or sulfonium salts substituted with organic radicals, and optionally also mixtures thereof. The letter n stands for a natural number. Oligomers having n>1 may also be used (in which case (n−1) R radicals act as bridges between two X), but monomeric ions (n=1) are preferred.
Ammonium, guanidinium, phosphonium, sulfonium and sulfoxonium ions having C
6
to C
18
aryl, C
7
to C
18
aralkyl or C
1
to C
20
alkyl radicals as organic radicals are suitable for use in the process according to the invention. The radicals in each case may be all the same or different and may themselves be substituted. Any two substituent radicals may be replaced by a ring, and mixtures of several quaternary cations may optionally also be used.
The following ions may be listed by way of examples: tetramethyl ammonium, tetra-n-ethyl ammonium, tetra-n-propyl ammonium, tetra-n-butyl ammonium, di-n-decyl dimethyl ammonium, di-n-octadecyl dimethyl ammonium, tri-n-decyl methyl ammonium, N-methyl-N-decyl morpholinium, N-methyl methyl pyrrolidinium, N-(2-hydroxyethyl)-N-ethyl piperidinium, benzyl tributyl ammonium, phenyl trimethyl ammonium, tetraphenyl ammonium, tetramethyl phosphonium, tetra-n-ethyl phosphonium, tetra-n-propyl phosphonium, tetra-n-butyl phosphonium, di-n-decyl dimethyl phosphonium, di-n-octadecyl dimethyl phosphonium, tri-n-decyl methyl phosphonium, benzyl tributyl phosphonium, phenyl trimethyl phosphonium, tetraphenyl phosphonium, hexaethyl guanidinium, tetramethyl bishexyl guanidinium.
Tetraalkyl ammonium ions, tetraaryl ammonium ions, tetraalkyl phosphonium ions, tetraaryl phosphonium ions and hexaalkyl guanidinium ions are preferably used. Tetrabutyl or tetraphenyl ammonium ions or tetrabutyl or tetraphenyl phosphonium ions are particularly preferably used, whereby tetrabutyl ammonium ions or tetraphenyl phosphonium ions are most particularly preferably used.
Halides, nitrates, sulfates, hydrogen sulfates, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, dihydrogen phosphates, tetrafluoroborates, perchlorates, carboxylates or hexafluorophosphates, for example, may be used as the counter-anion Y
m−
of the quaternary cations. The letter m stands for a natural number. Mixtures of different anions are possible. Halides are preferred, particularly preferably bromide.
Hexaalkyl guanidinium halides, tetraalkyl ammonium ha

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