United States Patent (19) 11 Patent Number: 4,698,448 Ude et al. 45 Date of Patent: Oct. 6, 1987 54 METHOD FOR MAKING AROMATIC 3231331 3/1984 Fed. Rep. of Germany . PHOSPHORUS COMPOUNDS 1561198 2/1980 United Kingdom. 75) Inventors: Werner Ude, Darmstadt; Siegmund OTHER PUBLICATIONS Besecke, Seeheim-Jugenheim; Achim Kosolapoff et al, Organic Phosphorus Compounds, Riemann, Marburg; Guenther Wiley InterSc., N.Y., vol. 1, pp. 60 & 61 (1972). Schroeder, Ober-Ramstadt, all of Kosolapoff et al, Organic Phosphorus Compounds, Fed. Rep. of Germany Wiley InterSc., N.Y., vol. 3, pp. 379-383 (1972). (73) Assignee: Röhm GmbH, Darmstadt, Fed. Rep. Kosolapoff et al, Organic Phosphorus Compounds, of Germany Wiley-InterSc., vol. 4, pp. 15, 16 and 44 (1972). Chem. Abstr. 52, 20038a (1958). 21 Appl. No.: 751,625 Chem. Abstr, 87, 40281v (1977). 22 Filed: Jul. 2, 1985 Chem. Abstr. 83, 43459n (1975). Chem. Abstr. 96, 6000d (1982). 30 Foreign Application Priority Data J. Org. Chem 42(12), 10 (1977). Jul. 10, 1984 DE Fed. Rep. of Germany ....... 3.425282 Chem. Ber. 102 (9), 2922-2929 (1969). 51) Int. Cl'................................................ CO7F 9/53 Chem. Ber. 102 (9), 2914-2921 (1969). 52 U.S. C. ........................................ 568/14: 568/15; Primary Examiner-Helen M. S. Sneed 568/16; 568/17 Attorney, Agent, or Firm-Curtis, Morris & Safford 58) Field of Search ........................ 568/16, 17, 14, 15 57 ABSTRACT 56) References Cited Compounds of the formula U.S. PATENT DOCUMENTS 2,138,835 12/1938 Butz .................................. 568/14 X (m 2,902,517 9/1959 Schmerling ........................... 568/17 X-Air - Ar-X, 3,032,589 5/1962 Hoffmann et al. .... ... 568/14X 3,331,878 7/1967 Priestley ............ ... 568/17 X R 3,450,772 6/1969 Bridger et al. ...................... 260/63 4,052,463 10/1977 Uhing et al. .......................... 568/14 4,087,408 5/1978 Moedritzer ........ ... 568/15 X wherein R is lower alkyl or aryl, Y is oxygen or sulfur, 4,447,584 5/1984 Bergeret et al.... ... 568/14 X m is 0 or 1, Ar is arylene, and X is halogen, methyl, or 4,463,159 7/1984 Besecke et al. ..................... 528/167 aryloxy, or polymers containing repeating units of this 4,472,570 9/1984 Besecke et al. .... 528/167 kind are prepared from a compound R-P(Y)Cl2, 4,492,805 1/1985 Besecke et al. ..................... 568/O12 where r is 0 or 1 but is never greater than m, by reaction with one or two molar parts of a compound H-ArX in FOREIGN PATENT DOCUMENTS the presence of a Friedel-Crafts catalyst. 1238024 4/1967 Fed. Rep. of Germany . 3203186 8/1983 Fed. Rep. of Germany . 2 Claims, No Drawings 4,698,448 1 2 fire hazard due to the use of ether, and the risk that METHOD FOR MAKING AROMATIC explosive peroxides may form. PHOSPHORUS COMPOUNDS It is further known to form an aromatic/phosphorus bond through a Friedel-Crafts reaction. Thus, V. V. The present invention relates to methods for making 5 certain aromatic phosphorus compounds, and to such Korschak (Isvestija Akademi Nauk USSR, Otdel, compounds. Chim. 1958, pp. 595-601) reacted para-chlorophenyldi Phosphorus-containing polyarylene ethers having chlorophosphine with dibenzyl in the presence of alu repeating units of the structure minum chloride to give oligomeric compounds with O repeating units of the structure (9) O-Air', -CH-CH-CH- CH2 P C6H4C R 15 These oligomers do not have the desired polyether wherein R' is alkyl or aryl, Ar' is a bivalent aromatic structure shown herein at the outset, nor are they suit group, and q is 0 or 1, are known from published Ger able for use as intermediates in the preparation of such man patent application DOS No. 3203 186 as difficultly 20 polyethers. combustible or noncombustible plastics having resis 6. In published German patent application DAS No. tance to high temperatures and a high softening temper 1,238,024, arylated phosphorus/thio compounds are ature. prepared from trichlorophosphine sulfide or its deriva The present invention relates to a new method for making such polyarylene ethers or to monomeric start tives in which one or two chlorine atoms are replaced ing compounds for such polyarylene ethers. The pro 25 by organic groups, and aromatic hydrocarbons in the cess involves a Friedel-Crafts reaction. presence of aluminum chloride or other Friedel-Crafts According to the aformentioned published German catalysts. The chlorine atoms contained in the chlori patent application, the polyarylene ethers there named nated phosphine sulfide used are replaced by aromatic are obtainable, for example, by the reaction of equimo 30 nuclei. However, this synthesis produces neither poly lar amounts of di(fluorophenyl)phenylphosphine oxide mers nor starting materials from which phosphorus and of an aromatic diol such as dioxydiphenyl ether, containing polyarylene ethers can be obtained accord with cleavage of hydrogen fluoride in the presence of a ing to published German patent application DOS No. base. The di(fluorophenyl)phenylphosphine oxide and 32 O3 188. analogous starting compounds are prepared by reacting 35 the Grignard reagent of a brominated aromatic hydro G. Olah and D. Hehemann (J. Org. Chem., Vol. 42, carbon compound with dichlorophenylphosphine or 1977, p. 2190) have found that phosphorus trichloride dichlorophenylphosphine oxide in ether as the solvent, can be reacted in the presence of sulfur and of Friedel for example by the route Crafts catalysts with aromatic hydrocarbons to give good yields of triarylphosphine sulfides, which can be converted to the corresponding triarylphosphines by means of reducing agents. F Br + Mg - GF MgBr The present inventors set themselves the task of pre paring phosphorus-containing polyarylene ethers hav 45 ing the structure given earlier herein, or intermediates suitable for their preparation which contain a phospho 2F MgBr + Cl2P=(O)0 or 1) --G rus atom bound to two aromatic nuclei and which can be converted by known processes to phosphorus-con taining polyarylene ethers, in good yield from low-cost 50 starting materials by a process which is technically readily controllable. In a narrower sense, the object was to prepare in said (Q)(0 or 1) advantageous manner compounds of the formula 55 F P F (YOn (I) Xa-Ara- -A-x. R However, for a number of reasons the formation of a bond between the phosphorus atom and an aromatic nucleus by way of a Grignard reaction is not well suited wherein R is lower alkyl or aryl, Y is oxygen or sulfur, for a commercial process, regardless of whether the m is 0 or 1, Ar is arylene, and X is halogen, methyl, or latter is to be used directly for the production of poly aryloxy. The compounds will be phosphorus-containing mers or for the preparation of monomeric starting mate 65 polyarylene ethers if X is an aryloxy group which in rials therefor. Among these reasons are the necessity of turn is linked to a further unit having the structure using expensive bromine compounds, ether, and metal represented in the formula, as in polymers with repeat lic magnesium, the high sensitivity of the reaction, the ing units of the structure 4,698,448 4. compound of the formula H-ArX in the presence of a Friedel-Crafts catalyst. The compounds of formula (I) wherein m=1 and Y = sulfur are new substances which, when polymerized, form synthetic resins having valu able properties. The phosphorus-containing starting compound "Aryl' in this case symbolizes a bifunctional aromatic R-POY)Cl2 may, depending on the presence and na group which may be different from the group repre ture of the group Y, be sented by Ar. For example, it may be a phenyl group or (A) a dichlorophosphine, R-PCl2, a polynuclear aromatic group having the structure 10 (B) a dichlorophosphine oxide, R-POCl2, or (C) a dichlorophosphine sulfide, R-PSCl2. The reactivity, and hence the preferability in the pro -(Aro) cess of the invention, increases from dichlorophosphine R' -, oxide to dichlorophosphine to dichlorophosphine sul 15 fide. The reactivity of dichlorophosphine (A) will cor respond to that of dichlorophosphine sulfide (C) if the wherein R' is a covalent single bond, oxygen, sulfur, reaction is carried out in the presence of elemental sul carbonyl, sulfonyl, methylene, or isopropylidene, or fur, in which case a product of the formula (I) with a 20 P=S bond (m=1, Y=S) is formed by sulfonation. The O reactivity of dichlorophosphine oxide is markedly I lower and satisfactory only for reaction with aromatic -P-, compounds of the formula H-Ar-O-Aryl to give polymeric products of the formula (I). For reaction with other aromatic compounds H-ArX, compounds 25 of types (A) and (C) therefore are highly preferable. The group R may be lower alkyl which as a rule contains not more than 4 carbon atoms. Methyl groups preferably oxygen or isopropylidene. Bridging groups are preferred. R is preferably an aryl group, and more R" free of hydrogen are preferred. n is an integer, at particularly an unsubstituted phenyl group. least 1 and generally not greater than 10, preferably 1 to 30 Phosphine compounds of the types (A), (B) and (C) 5. When n is greater than 1, the groups R' may be are known in the art and are obtainable by Friedel different. The terminal phenyl groups are preferably Crafts arylation of the corresponding phosphorus tri attached to an oxygen or sulfur atom or to a methylene chlorides or by the reaction of such trichlorides with or isopropylidene group. p is 0 or 1. alkyl halides. However, formula (I) may also represent intermedi 35 The aromatic compound H-ArX will usually con ate products which can be converted into phosphorus tain a phenyl group unsubstituted in the ortho position containing polyarylene ethers either directly or after or, preferably, in the para position.