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United States Patent (19) 11 4,311,652 Abramson Et Al

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United States Patent (19) 11 4,311,652 Abramson Et Al United States Patent (19) 11 4,311,652 Abramson et al. 45 Jan. 19, 1982 54 ARBUZOV REACTIONS EMPLOYING AN 56) References Cited ALEPHATIC SOLVENT U.S. PATENT DOCUMENTS 3,483,279 12/1969 Davis et al. ......................... 260/969 75 Inventors: Alan Abramson, White Plains; 3,699,193 10/1972 Melton ..... ... 260/969 Edward D. Weil, 3,776,984 12/1973 Ratts ................................... 260/969 Hastings-on-Hudson, both of N.Y. Primary Examinter-Anton H. Sutto Attorney, Agent, or Firm-Vivienne T. White 73 Assignee: Stauffer Chemical Company, 57 ABSTRACT Westport, Conn. An improved process for phosphite rearrangement wherein the phosphite is rearranged to the phospho nate. The improvement comprises conducting the phos 21 Appl. No.: 154,170 phite rearrangement reaction in an aliphatic solvent which is miscible with the reactants at reaction temper atures, and immiscible with the product at lower tem 22 Filed: May 28, 1980 peratures. Increased yields of the phosphonate product are obtained without the need for additional distillation 51 int. Cl. ................................................ C07F 9/40 for solvent separation. 52 U.S. C. ................ ... 260/969; 260/990 58 Field of Search ................................ 260/969, 990 12 Claims, No Drawings 4,311,652 3 4. The advantage of conducting the rearrangement in a process for rearranging tris(2-chloroethyl) phosphite. solvent were found to be a more easily controlled exo The invention is directed to phosphite rearrangements, therm due to the heating and reflux of the solvent which wherein the novel process comprises conducting the removes the heat of reaction, and inhibiting the degra rearrangement process in an essentially aliphatic Solvent dation of the phosphonate product produced. Solvents 5 which is miscible with the reactants at the reaction mentioned in the prior art as being suitable for use in temperature, but substantially immiscible with the phos such rearrangement reactions were those disciosed in phonate product at lower temperatures. One advantage U.S. Pat. No. 2,725,311. of the novel process is the simple and economical sepa The aromatic solvents utilized in the prior art have, ration of the product from the solvent as by phase sepa however, required tedious distillation procedures to 10 ration in contrast with the prior art process which re separate the solvent from the product. In prior art con quired tedious and expensive distillative separation. tinuous rearrangement process using heat exchangers or stirred tanks, the product containing the solvent had to DETAILED DESCRIPTION OF THE be immediately removed, and continuously distilled INVENTION over a period of hours to remove the solvent. In the 15 The invention process disclosed herein is directed to process of stripping the solvent additional product the rearrangement of a phosphite to produce a phospho would be lost due to the formation of degradation prod nate. The invention is also desirably directed to the ucts. A byproduct such as ethylene dichloride from the rearrangement of tris(2-chloroethyl) phosphite to form production of bis(2-chloroethyl) 2-chloroethylphos bis(2-chloroethyl) 2-chloroethyl phosphonate. phonate, for instance, during the vacuum distillation 20 The process of the invention comprises conducting process would deteriorate the vacuum, and cause the the rearrangement process in an essentially aliphatic temperature to increase resulting in further product solvent which is miscible with the reactant or reactants decomposition. This and other routes of decomposition, at the reaction temperature but substantially immiscible of 2-chloroethyl esters of phosphoric acids are disclosed with the product at lower temperatures. by Kafengauz et al. in Soviet Plastics, April 1967, pp. 25 The term "essentially aliphatic' is used herein to 73-75 wherein the formation of 1,2-dichloroethane, mean solvents which are comprised primarily of ali vinyl chloride, acetaldehyde and acidic residual prod phatic moieties as opposed to aromatic components. ucts are discussed. In addition to the distillation difficul Use of the term "substantially immiscible' means that ties, even after distillation appreciable amounts of the only small amounts of the phosphonate product are prior art aromatic solvent would remain in the product. 30 soluble in the solvent at room temperature. U.S. Pat. No. 2,725,311 disclose the use of solvents in The variation in solubility of the reactants and prod the preparation of the phosphonate product by a pro uct with temperature, allows the solvent to be removed cess in which phosphorus trihalide is reacted with alkyl by a simple phase separation. The disclosed process is ene oxide and the temperature is raised to 150 C. to therefore more convenient, and more economical than cause the rearrangement. Suitable solvents were dis 35 the distillation separation which would normally be closed to be o-dichlorobenzene, aromatic mineral spir required when using solvents disclosed in the prior art. its, ethanol, or those solvents capable of dissolving the The intramolecular rearrangement of the phosphite phosphonate which are easily volatized. - to form the phosphonate product using the solvents U.S. Pat. No. 4,144,387 discloses the slow addition of disclosed herein is applicable to known batch or contin tris(2-chloroethyl) phosphite to a product heel (i.e., a 40 uous production methods. heel of the preformed product) at a temperature below Solvents suitable for use in the novel process dis 180° C. to avoid side reactions such as polymerization. closed herein are aliphatic and preferably alkane sol The initial heel is said to be produced by the autogenous vents such as hexanes, heptanes, octanes, nonanes, dec reaction of the phosphite at 175 C. over a period of anes, dodecanes, tetradecanes, eicosanes and mixed hours using o-dichlorobenzene as the solvent. After the 45 alkanes as Soltrol (R) 170, which is a Phillips Petroleum initial heel was produced it was used in the subsequent Company brand of a mixed aliphatic hydrocarbon sol production process to form additional phosphonate vent. The selection of alkanes boiling above 140 C. product without any additional solvent. This method is permits the use of atmospheric pressure or high pres said to eliminate the need for using the inert solvent in Se. the final product run, which would necessitate expen 50 The use of solvents which are mixtures of aromatic sive solvent separation. and aliphatic hydrocarbon are also within the scope of The object of the invention disclosed herein is to the invention if they are predominantly aliphatic and provide a means whereby the thermal isomerization of meet the criteria of being miscible with the reactant or the phosphite can be accomplished to form the phos the reactants at the reaction temperature and are essen phonate product, without the necessity of further distil 55 tially or substantially immiscible with the phosphonate lation to remove the solvent. - product at lower temperatures. Ashland Chemical Another object of the invention is the production of Company's low odor base solvent (primarily comprised high quality bis(2-chloroethyl) 2-chloroethyl phospho of isoparafin hydrocarbons with about 4% aromatics nate by the rearrangement of tris(2-chloroethyl) phos and traces of olefin) is a suitable solvent for use in the phite using a solvent which can be conveniently and 60 process. economically removed from the product. Solubility tests conducted on tris(2-chloroethyl) Other objects of the invention or advantages of the phosphite and bis(2-chloroethyl) 2-chloroethylphos invention will be evident from the following disclosure. phonate at room temperatures showed that both were soluble in aromatic solvents. Similar solubility tests SUMMARY OF THE INVENTION 65 indicated that heptane is a poor solvent for both the The invention is a novel process for performing the phosphite ester and the phosphonate product at ambient Michaelis-Arbuzov or Arbuzov rearrangement, desir temperatures, but on warming to about 70° C. the phos ably a haloalkyl phosphite, and in particular, it is a novel phite was found to be very soluble whereas the phos 4,311,652 1. 2 instance of R", it is critical that the halogen (X) be ARBUZOV REACTIONS EMPLOYING AN attached to a carbon atom which is a beta carbon with ALIPHATIC SOLVENT respect to the oxygen moiety, or to a carbon atom which is further removed from the oxygen moiety. The BACKGROUND OF THE INVENTION 5 moieties other than those illustrated above do not par 1. Field of the Invention ticipate in this reaction and hence their identity is not The present invention relates to a novel method of critical. carrying out Michaelis-Arbuzov or Arbuzov type rear For example, reaction goes forward with phosphite rangements, and more particularly, it relates to the auto esters: geneous rearrangement of tris(2-chloroethyl) phosphite O to bis(2-chloroethyl) 2-chloroethylphosphonate. R-O 2. Prior Art )P-O-R or Michaelis-Arbuzov reactions have long been known, R-O having been first described in J. Russ. Phys. Chem. Soc. Vol. 38, 687 (1906). As a result of extensive investiga 5 with phosphonite esters: tions in the field it has come to be accepted that the Michaelis-Arbuzov reaction in its simplest form com R R prises the reaction with rearrangement of a phosphite a P-O-R or with an organic halide, to obtain a phosphonate. An R-O illustrated equation is as follows: with the phosphinite esters: O DP-O-R + RX --> R 25 R P-O-R-X wherein R is an alkyl or substituted alkyl radical, X is or expressed more generically, with any compound of halogen and R' is an alkyl or substituted alkyl having at its point of attachment to X an aliphatic carbon atom. the formula: If R and R' are identical only catalytic quantities of 30 RX are required to cause rearrangement of the phos phite to phosphonate. On the other hand, where R and R" are different, a stoichiometric amount of RX is re quired to prepare the desired phosphonate product.
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