Process for the preparation of DOPO-derived compounds and compositions thereof
This invention relates to a process for producing compounds derived from 9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-oxide (DOPO). In particular, the invention relates to producing DOPO-derived compounds by reacting DOPO with diol compounds in the presence of a catalyst. This invention also relates to DOPO derived composition containing a high melting point diastereomer. The DOPO derived compounds may be useful as flame-retardants.
1. A process for preparing a compound of Formula I:
wherein each R 1 , R 2 , R 3 and R 4 are independently hydrogen, C 1 -C 15 alkyl, C 6 -C 12 aryl, C 7 -C 15 aralkyl or C 7 -C 15 alkaryl; or R 1 and R 2 or R 3 and R 4 taken together form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring is optionally substituted by a C 1 -C 6 alkyl; each m is independently 1, 2, 3 or 4; and n is 2 to about 18;
comprising reacting a compound of Formula A with a diol compound of Formula B in the presence of a catalyst, optionally a solvent, and optionally an entrainer:
wherein R 3 , R 4 and m are defined above;
HO—(CH 2 ) n —OH Formula B
wherein n is defined above.
2. The process of claim 1 , wherein n is 2 to 6 and R 1 , R 2 , R 3 and R 4 are hydrogen.
3. The process of claim 1 , wherein both the solvent and the entrainer are present.
4. The process of claim 1 , wherein said catalyst is an alkyl halide, an alkali halide, an alkaline earth metal halide, a transition metal, a transition metal halide, or an acid catalyst.
5. The process of claim 1 , wherein the reaction takes place at a temperature ranging from about 100° C. to about 250° C.
6. The process of claim 1 , wherein the reaction takes place in a reactor, the reaction produces water, and wherein the water and the diol compound of Formula B are continuously recycled back to the reactor.
7. The process of claim 1 , wherein the catalyst is an acid catalyst.
8. The process of claim 7 , wherein said acid catalyst is sulfuric acid, aryl sulfonic acid, alkyl sulfonic acid, aralkyl sulfonic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, perchloric acid, trifluoromethane sulfonic acid, fluorosulfonic acid, nitric acid, aluminum chloride, diethyl aluminum chloride, triethylaluminum/hydrogen chloride, ferric chloride, zinc chloride, antimony trichloride, stannic chloride, boron trifluoride, acidic zeolites, acidic clays, polymeric sulfonic acids, or mixtures thereof.
9. A process for preparing a compound of Formula II:
comprising reacting a compound of Formula C with ethylene glycol in the presence of a catalyst, optionally a solvent, and optionally an entrainer:
10. A method of increasing a content of high melting point isomers in a mixture of stereoisomers comprising contacting a composition containing initial amounts of high melting point diastereomers of Formula IIa, and initial amounts of low melting point enantiomers of Formulas IIb and IIc:
with alcohols, water, or mixtures thereof, in the presence of an acid catalyst to convert at least a portion of the low melting point enantiomers of Formulas IIb and IIc to high melting point diastereomers of Formula IIa.
11. The method of claim 10 , wherein said acid catalyst is sulfuric acid, aryl sulfonic acid, alkyl sulfonic acid, aralkyl sulfonic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, perchloric acid, trifluoromethane sulfonic acid, fluorosulfonic acid, nitric acid, phosphoric acid, phosphonic acids, phosphinic acids, aluminum chloride, diethyl aluminum chloride, triethylaluminum/hydrogen chloride, ferric chloride, zinc chloride, antimony trichloride, stannic chloride, boron trifluoride, acidic zeolites, acidic clays, polymeric sulfonic acids, or mixtures thereof.