Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-11-08
2003-08-19
Keys, Rosalynd (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S613000, C568S615000, C568S618000, C568S619000, C568S672000, C568S678000, C568S679000, C568S680000, C568S695000, C560S179000, C560S186000, C560S187000, C562S008000, C562S020000, C562S036000
Reexamination Certificate
active
06608230
ABSTRACT:
This invention relates to a single-stage process for the production of &agr;-hydroxy ethers by oxidation of C═C unsaturated compounds with hydroperoxides in the presence of a mono- or polyhydric alcohol as a nucleophile and solvent, wherein systems based on molybdenum compounds with boron trifluoride or alumina or 1,8-diazabicyclo-[5.4.0]-undec-7-ene or 1,4-diazabicyclo-[2.2.2]-octane are used as catalysts.
Industry has an interest in &agr;-hydroxy ethers, for example those represented by formulae (I) and (II). The compounds according to formula (I) may be employed in cosmetics, as lubricants for synthetic resins, in emulsion paints, as solvents, and as surfactants or co-surfactants.
The compounds according to formula (II) belong to the group of gemini surfactants, such as those described in WO 96/16033. These compounds according to formula (II) either serve as precursors of the ionic and nonionic, amphiphilic compounds referred to in WO 96/16033, or may be used as emulsifiers, demulsifiers, auxiliaries in metal working, ore mining, or surface finishing, as textile auxiliaries, or for cleaning and washing textiles or hard surfaces, and for washing and cleaning skin and hair.
R
1
, R
2
, R
4
, and R
6,
independently of one another, are saturated, unbranched or branched hydrocarbon radicals, or are completely or partially fluorinated hydrocarbon radicals having 1 to 22 carbon atoms, preferably 8 to 18 carbon atoms. In detail, the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-henicosyl, n-docosyl, and the branched-chain isomers thereof or their completely or partially fluorinated hydrocarbon radicals are referred to herein.
R
3
represents mono- or polyhydric, linear or branched radicals of alcohols having 1 to 22 carbon atoms which may also be fluorinated wholly or in part. Examples include methanol, ethanol, n- and iso-propanol, n- and iso-butanol, pentanol, hexanol, heptanol, n-octanol, 2-ethyl hexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, trimethylol propane, neopentyl glycol, glycerol, and trifluoroethanol and mixtures thereof. Among long-chain alcohols, particularly those compounds with even carbon numbers are preferred. R
5
is a spacer consisting of an unbranched or branched chain with 2 to 100 carbon atoms which contains 0 to 20 oxygen atoms, 0 to 20 nitrogen atoms, 0 to 4 sulfur atoms, and 0 to 3 phosphorus atoms, and which has 0 to 20 functional side groups, such as hydroxyl, carbonyl, carboxyl, amino and/or acylamino groups. Said spacer is described in greater detail in WO 96/16033 incorporated by reference herein.
X and Y, independently of one another, are substituents according to formula XVI
—(C
2
H
4
O)
&agr;
(C
3
H
6
O)
&bgr;
H (XVI)
where
&agr;=0 to 50, preferably &agr;=10 to 30,
&bgr;=0 to 60, preferably &bgr;=20 to 40,
and
&agr;+&bgr;=1 to 100, preferably
&agr;+&bgr;=10 to 50,
and wherein the alkoxide units are incorporated randomly or blockwise and the sequence is optional,
or are substituents according to formula XVII
—(C
2
H
4
O)
&ggr;
(C
3
H
6
O)
&dgr;
—FR (XVII)
where each
&ggr;=0 to 20, preferably &ggr;=0 to 8,
&dgr;=0 to 20, preferably &dgr;=0 to 12,
and
&ggr;+&dgr;=0 to 40, preferably
&ggr;+&dgr;=5 to 20,
and FR represents a functional radical
—CH
2
—COOM, —SO
3
M, —P(O(OM)
2
,
—C
3
H
6
—SO
3
M, or
—O—C(O)—C
2
H
3
(SO
3
M)—CO
2
M′,
wherein M, M′ are equal to alkali, ammonium, alkanol ammonium, or ½ alkaline earth metal.
In each case the degree of alkoxylation is a mean which, within the defined limits, can be any value, including a non-integral one.
Prior-art processes for the production of said hydroxy ethers from olefins comprise two stages. At first, the olefin is epoxidized with a suitable oxidant and then purified. Per-acids are employed as oxidants for the epoxidation of long-chain olefins. Using silver catalysts, ethylene and butadiene can directly be reacted with oxygen to yield the corresponding epoxides. The customary method for producing propylene oxide is by molybdenum-, vanadium-, or titanium-catalyzed epoxidation of propylene with hydroperoxides. Although it is well known from literature that long-chain epoxides, too, can be epoxidized by the so-called Halcon (or oxirane) process [for example, cf. R. A. Sheldon,
J. Mol. Catal.,
7 (1980), 107], said process has not been employed hitherto for this purpose. In the second stage of the process for producing &agr;-hydroxy ethers the epoxides are opened with an alcohol usually in the presence of a catalyst. Since epoxides are rather expensive, they are rarely utilized for industrial processes. Thus, there remained a pressing need for a process which does not require expensive raw materials and wherein the epoxide stage occurs as an intermediate stage.
The opening of the oxirane ring is fairly easy with short-chain epoxides, such as ethylene oxide or propylene oxide, but requires ever-severer reaction conditions with increasing chain lengths. Both acids and bases are suitable as catalysts. In practice, classical Bronsted acids, such as H
2
SO
4
[see R. A. Wohl,
Chimie,
28 (1974) 1; DE 38 29 735], a large number of different Lewis acids [see e.g. P. Gassmann, T. Guggenheim,
J. Am. Chem. Soc.,
104 (1982) 5849; M. Bischoff, U. Zeidler, H. Baumann, Fette, Seifen,
Anstrichmittel,
79 (1979) 131], heteropolyacids [see e.g. Y. Izumi, K. Hayashi,
Chem. Lett.
(1980) 787], and Al
2
O
3
[cf. G. H. Posner,
Angew. Chem.,
90 (1978) 527] as well as sulfuric acid-treated phyllosilicates [cf. S. Hellbardt, K. Schlandt, W. H. Zech, DE 42 03 077] have been employed. However, the latter ones require significantly higher temperatures (>130° C.).
There are only few experiments known from literature which describe the production of &agr;-hydroxy ethers from olefins by a single-stage synthesis. U.S. patent specification 2,808,442 describes the wolfram-catalyzed direct synthesis of &agr;-hydroxy ethers by reaction with a 35% to 100% hydrogen peroxide. The water which is inevitably present results in the formation of vicinal diols. Therefore, when using a 35% hydrogen peroxide, the &agr;-hydroxy ethers are defined as mere by-products. Titanium silicalites, too, have been used as catalysts for the direct synthesis of &agr;-hydroxy ethers from olefins and alcohols using hydrogen peroxide (cf. GB 2 252 556), but the problem of competing ring opening due to the presence of water persists.
Hence, it is the object of the present invention to develop a process for the direct, single-stage production of &agr;-hydroxy ethers which process is carried out in the absence of water, thus preventing the competing production of diol which is regarded as the main disadvantage of the processes described hereinabove.
According to the present invention, the problem is solved by using
organic hydroperoxides, ROOH, as oxidants
homogeneous or heterogeneous molybdenum compounds as a first catalyst component
boron trifluoride in the form of a stabilized complex, or an alumina, or 1,8-diazabicyclo-[5.4.0]-undec-7-ene, or 1,4-diazabicyclo-[2.2.2]-octane as a second catalyst component
mono- or polyhydric alcohols as nucleophiles and, simultaneously, as solvents without precluding the use of other solvents.
Therefore, the subject matter of the present invention is a single-stage process for the production of &agr;-hydroxy ethers according to formulae (I) and (II) which process is performed by the oxidation of olefinic substrates with organic hydroperoxides and opening of the resultant oxirane ring using mono-
Klaas Mark Rüsch gen.
Kwetkat Klaus
Warwel Siegfried
Zillmann Hans-Martin
Browning & Bushman P.C.
Keys Rosalynd
WE-DEA Aktiengesellschaft für Mineraloel und Chemie
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