Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus esters
Patent
1992-11-13
1994-04-12
Lee, Mary C.
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus esters
568 13, C07F 940, C07F 952
Patent
active
053027388
DESCRIPTION:
BRIEF SUMMARY
The present invention is concerned with novel, racemic and optically active phosphorus compounds of the general formula ##STR2## wherein R signifies lower alkyl, lower alkoxy or protected hydroxy, R.sup.1 signifies lower alkoxy, phenoxy, benzyloxy, chlorine or bromine, R.sup.2 stands for lower alkyl or lower alkoxy and n represents the number 0, 1 or 2.
The invention is also concerned with the manufacture of the phosphorus compounds of formula I.
The term "lower alkyl" signifies in the scope of the present invention straight-chain or branched alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert.butyl. The term "lower alkoxy" signifies groups in which the alkyl residue has the foregoing significance. The terms "phenoxy" and "benzyloxy" signify in the scope of the present invention substituents in which the phenyl residue can be not only unsubstituted, but also substituted in the meta- or para-position or also poly-substituted. Lower alkyl groups, preferably methyl groups, especially come into consideration here as substituents. As protecting groups for the hydroxy group there come into consideration in the scope of the present invention especially the usual ether-forming groups such as e.g. benzyl, allyl, benzyloxymethyl, lower alkoxymethyl, 2-methoxyethoxymethyl and the like.
The phosphorus compounds of formula I can be present not only in racemic form, but also in optically active form. Of those compounds of formula I in which R represents lower alkyl the optically active compounds are preferred.
Preferred compounds of formula I are, moreover, those in which n stands for the number 0, R.sup.1 signifies phenoxy, ethoxy or chlorine and R represents methoxy, methoxymethyl or methyl, especially methoxy.
Especially preferred compounds of formula I are:
(RS)-(6,6'-Dimethoxybiphenyl-2,2'-diyl)bis(phosphonic acid diphenyl ester),
(R)- or (S)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(phosphonic acid diphenyl ester),
(RS)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(phosphonic acid diethyl ester),
(R)- or (S)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(phosphonic acid diethyl ester),
(RS)-[6,6'-bis(methoxymethoxy)biphenyl-2,2'-diyl]bis(phosphonic acid diphenyl ester),
(R)- or (S)-[6,6'-bis(methoxymethoxy)biphenyl-2,2'-diyl]bis(phosphonic acid diphenyl ester),
(RS)-(6,6'-dimethylbiphenyl-2,2'-diyl)bis(phosphonic acid diphenyl ester),
(R)- or (S)-(6,6'-dimethylbiphenyl-2,2'-diyl)bis(phosphonic acid diphenyl ester),
(RS)-(6,6'-dimethylbiphenyl-2,2'-diyl)bis(phosphonic acid diethyl ester),
(R)- or (S)-(6,6'-dimethylbiphenyl-2,2'-diyl)bis(phosphonic acid diethyl ester),
(RS)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(phosphonic acid dichloride),
(R)- or (S)-(6,6'-imethoxybiphenyl-2,2'-diyl)bis(phosphonic acid dichloride).
The compounds of formula I in accordance with the invention can be manufactured, for example, by subjecting a compound of the formula ##STR3## wherein R, R.sup.2 and n have the above significance and R.sup.3 signifies lower alkoxy, phenoxy or benzyloxy, to an Ullmann coupling, if desired resolving a thus-obtained compound of the formula ##STR4## wherein R, R.sup.2, R.sup.3 and n have the above significance, which is present in the (RS) form into the (R) form and (S) form using dibenzoyltartaric acid or di-p-toluyltartaric acid and, if desired, replacing a lower alkoxy group denoted by R.sup.3 in a racemic or optically active compound of formula III by chlorine or bromine.
The conversion of a compound of formula II into a compound of formula III which is present in the (RS) form is effected in accordance with the invention by means of an Ullmann coupling. This is a reaction which is known per se and which can be carried out under the conditions which are usual for this. Thus, this reaction can be carried out, for example, by heating a compound of formula II in an inert organic solvent such as e.g. N,N-dimethylformamide with e.g. copper powder activated with iodine to a temperature of about 110.degree. C. to about 200.degree. C. If desired, the reaction can also be carried
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Greene, T. W. Protective Groups in Organic Synthesis; John Wiley and Sons: New York, 1981, pp. 10, 14-16.
Foricher Joseph
Heiser Bernd
Schmid Rudolf
Ambrose Michael G.
Epstein William H.
Gould George M.
Hoffmann-La Roche Inc.
Lee Mary C.
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