Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus acids or salts thereof
Reexamination Certificate
2000-05-25
2004-11-09
Anthony, Joseph D. (Department: 1714)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus acids or salts thereof
C558S089000, C558S104000, C568S008000, C524S133000
Reexamination Certificate
active
06815558
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention relates to a process for the preparation of (metal) salts of alkylphosphonous acids, and to the use of the (metal) salts of alkylphosphonous acids prepared by this process.
Organic phosphorus compounds are increasing in industrial importance. They are employed principally for the preparation of herbicides or as herbicides themselves, as extractants and as flame retardants. The starting materials used are preferably PH
3
and phosphorus halides, which must themselves in turn be prepared from yellow phosphorus.
The reaction of red phosphorus in the superbasic medium dimethyl sulfoxide/potassium hydroxide (DMSO/KOH) with acetylenes or olefins as alkylating agent (Trofimov et al., Phosphorus, Sulfur and Silicon 55, 271, 1991) preferentially gives triorganylphosphines and triorganylphosphine oxides.
The alkylation of red phosphorus using acrylonitrile under the abovementioned conditions with ultrasound treatment of the reaction mixture gives predominantly secondary phosphine oxide. If 1,1-diphenylethylene is employed, tert-phosphine oxide (30%), sec-phosphine oxide (10%) and phosphinic acid (35%) are obtained [D. Semenzin et al., Tetrahedron Letters 35, 3297, 1994].
It has also been attempted (Trofimov et al., Main Group Chem. News 4, 18, 1996, Phosphorus, Sulfur and Silicon, 109/110, 601, 1996) to react elemental phosphorus in its red modification with alkyl halides in the presence of potassium hydroxide, water, dioxane and a phase-transfer catalyst. The main product found comprised tert-phosphine oxides (up to 75% in the case of benzyl bromide, about 60-65% in the case of butyl bromide). As byproducts, sec-phosphine oxides and phosphinic acid esters are obtained with 19% and 6% respectively, but the former only in the presence of zinc powder as reducing agent.
However, the abovementioned processes have the disadvantage that first of all the red phosphorus or organophosphorus intermediates have to be prepared. The processes are technically very complex and consequently also not economical, and the products obtained often have to be purified subsequently at great effort. In particular, the specific preparation of certain compounds in high yield is frequently particularly difficult.
In addition, a number of starting materials, such as halogen-containing phosphorus compounds or phosphines, are unsuitable from the very beginning for a large-scale and economical process owing to their environmental toxicity.
SUMMARY OF THE INVENTION
There is therefore a demand for a process for the preparation of (metal) salts of alkylphosphonous acids which can be carried out in a simple manner and in which uniform products are obtained in high yield. A process of this type should also be clearly superior to those known hitherto in economic and environmental terms.
The invention therefore has the object of providing a process for the preparation of (metal) salts of alkylphosphonous acids which avoids the abovementioned disadvantages and with which the desired end products can be prepared without difficulty.
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Trofimov, Boris, et al., Phosphorus, Sulfur and Silicon, 1996, vols. 109-110, pp 601-604, Generation of Phosphide Anions from Phosphorus Red and Phosphine in Strongly Basic Systems to Form Organylphoshines and -Oxides, Overseas Publishers Association.
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Anthony Joseph D.
Bisulca Anthony A.
Clariant GmbH
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