Phosphorylation process and catalyst

Details Phosphorylation process and catalyst Phosphorylation process and catalyst

2000-10-16

2002-11-12

Wilson, James O. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carbohydrates or derivatives

C536S025330

Reexamination Certificate

active

06479656

ABSTRACT:

The present invention relates to a process and use of at least one Si, Ge or Sn comprising catalyst for phosphorylation, in particular phosphitylation, of hydroxyl groups. A phosphorous compound is added to a hydroxyfunctional compound having at least one hydroxyl group and said addition yields in the presence of said catalyst a phosphorous reaction product having at least one O—P bond.
The manufacture and use of phosphorous compounds, such as phosphates, phosphites and phosphides, are of substantial importance in areas including various animal die, fertilisers, detergents, pharmaceuticals, plasticisers, antioxidants, flame retardants and the like.
Phosphorylation of hydroxyfunctional compounds is known to be performed using phosphorous acids, whereby the phosphorus containing groups react with hydroxyl groups and other similar procedures.
Phosphorylations comprising a reaction between for instance an amide of a phosphorous acid and a hydroxyfunctional compound, as illustrated by the simplified reaction scheme (a) below
wherein each R independently can be alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, thiolo and the like, proceed very slowly and with exceptionally low yield, often as low as 20% or less, and a catalyst is normally used. A frequently used catalyst is tetrazole. derivatives thereof and structural analogues. The yield is thereby increased, but still very low, normally less than 50%. The use of tetrazole and its derivatives as catalysts exhibit, besides the low yield a number of drawbacks such as
the amount of tetrazole must be optimised in every case,
excess of tetrazole must be used,
formation of side products, usually derivatised from disproportionations,
problems caused by separation, and
freshly sublimed tetrazole must be used,
tetrazole is very expensive making large scale syntheses impossible
tetrazole is difficult, inconvenient and hazardous to handle.
Through the present invention, it has quite unexpectedly been found that a range of compounds, not previously employed as catalysts in phosphitylations and phosphorylations, substantially improve reaction time and yield. The yield is for instance in comparison to tetrazole increased from less than 50% to 80-100%, normally 90-95%.
The present invention refers to a process for phosphorylation, in particular a phosphitylation, of hydroxyl groups and use of at least one Si, Ge or Sn comprising catalyst during said process, whereby a phosphorous compound such as an amide of a trivalent phosphorous acid reacts with a hydroxyfunctional compound yielding a phosphorous reaction product having at least one O—P bond. The process is performed in the presence of at least one catalyst of general formula (1):
(R
1
)
n
X(R
2
)
4−n
  Formula (1)
wherein
i) each R
1
independently is
a) hydrogen,
b) at least one alkanyl, alkenyl, alkynyl, cycloalkanyl, cycloalkanyl, cycloalkynyl, aryl, alkanylaryl, alkenylaryl, alkynylaryl, trityl, alkoxy, cycloalkoxy, aryloxy or amino group,
c) a polymeric moiety derived from a carbon polymer or copolymer,
d) at least one halogenated and/or silylated alkanyl, alkeninl, alkynyl cycloalkanyl, cycloalkenyl, cycloalkynyl, aryl, alkanylaryl, alkenylaryl, alkynylaryl, trityl, alkoxy, cycloalkoxy, aryloxy or amino group, and/or
e) a polymeric moiety derived from a halogenated and/or silylated carbon polymer or copolymer;
ii) X is Si, Ge or Sn;
iii) each R
2
independently is a leavening group and is
a) F, Cl, Br or l; or
b) a sulphonate group of general formula (2)
 wherein R
3
is F, Cl, Br, I, alkanyl, alkenyl, alkynyl, aryl, arylalkanyl, arylalkenyl, arylalkynyl, haloalkanyl, haloalkenyl, haloalkynyl, haloaryl, haloarylalkanyl, haloarylalkenyl, haloarylalkynyl, arylhaloalkanyl, arylhaloalkenyl, arylhaloalkynyl or a group of formula CR
4
, wherein R
4
is F
3
, Cl
3
, Br
3
or I
3
;
iv) n is 1, 2 or 3.
The reaction performed during the process and activated by the compound of Formula (I) can be exemplified by below reaction scheme (b) illustrating the phosphitylation of thymidine using trimethylchlorosilane as catalyst:
Reaction Scheme (b)
Activation by a catalyst in accordance with the present invention requires normally one equivalent or less. The reaction is fast. often 30 minutes to 2 hours at 20° C., and free of side products. The yield is excellent, in most cases 95-100% and the resulting products are essentially pure requiring no further purification,
In preferred embodiments of the invention is each R
1
individually methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octal, nonyl, decyl, methylethyl, methylbutyl, methylisobutyl, methylpropyl, methylisopropyl, methyloctyl, methylphenyl, methyltrityl, allylmethyl, allylethyl, ethylbutyl, ethylisobutyl, ethylpropyl, ethylisopropyl, butylphenyl, butylmethoxyphenyl, ethoxy, propoxy, butoxy, ethoxymethyl, ethoxyethyl, thexylmethyl, phenyl, benzyl, xylyl, thexyl, thexylethyl, methyltrityl, butylmethylene, butylphenoxymethyl, methoxymethyl, vinyl, vinylmethyl, vinylethyl, vinylethoxy, cyanomethyl, cyanoethyl, halomethyl, haloethyl, halobutyl, halopropyl, halopentyl, halohexyl, haloheptyl, haloctyl, halononyl, halodecyl, halophenyl, halobenzyl, haloxylyl, halothexyl, methylhalohexyl, halophenylmethyl, butylhalophenylmethyl, halovinyl, vinylhalomethyl or vinylhaloethyl. At least one R
1
can in these and other preferred embodiments can be a moiety derived from, for example an analogue of, an organic polymer or copolymer, such as polyethylene, a polystyrene, a polyether or a polyester, or any analogues thereof, which polymer optionally is silylated and/or halogenated. X is in these and other especially preferred embodiments preferably Si.
Employed catalyst is in especially preferred embodiments a trialkylhalosilane, such as a trialkylchlorosilane, trialkyliodosilane, trialkylbromosilane or trialkylfluorosilane preferably selected from the group consisting of trimethylchlorosilane, triethylchlorosilane, tributylchlorosilane, tripropylchlorosilane, trimethyliodosilane, triethyliodosilane, tributyliodosilane, tripropyliodosilane, trimethylbromosilane, triethylbromosilane, tributylbromosilane, tripropylbromosilane, trimethylfluorosilane, triethylfluorosilane, tributylfluorosilane, tripropylfluorosilane.
Further compounds, advantageously being used as catalysts in accordance with the present invention, of Formula (I) wherein X is Si are suitably exemplified by trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, trimethylsilyltrichloroacetate, trimethylsilyltrifluoroacetate, allyldimethylchlorosilane, bromomethyldimethylchlorosilane, tert-butyldimethylchlorosilane, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide. N,O-bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyl-heptafluorobutyramide, N-methyl-N-trimethylsilyltrifluoroacetamide, trimethylsilyltrifluoromethanesulphonate, tert-butyldimethylsilyltrifluoromethanesulphonate, tert-butyldiphenylchlorosilane, tert-butyl-methoxy-phenylbromosilane, chloromethyldimethylchlorosilane, dimethyl(3,3,4,4,5,5,6,6,6-nonafluorohexyl)chlorosilane, dimethylphenylchlorosilane, dimethyltritylbromosilane, diphenylmethylchlorosilane, isopropyldimethylchlorosilane, (pentafluorophenyl)dimethylchlorosilane, thexyldimethylchlorosilane, thexyldimethylsilyl trifluoromethanesulphonate, tributylchlorosilane, triethylchlorosilane, trithylsilyltrifluoromethanesulphonate, triisopropylchlorosilane, triisopropylsilyltrifluoromethanesulphonate, triphenylchlorosilane, tripropylchlorosilane, di-tert-butyldichlorosilane, di-tert-butylsilyl bis(trifluoromethanesulphonate), diethyldichlorosilane, diisopropylsilyl-bis(trifluoromethanesulphonate), dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, dimethyloctylchlorosilane, dodecyltrichlorosilane, thexyldimethylsilyl-trifluoromethanesulphonate, thexyl-dimethylchlorosilane, trichlorosilan, 3-(triethylsilyl)propyl-trimethylammoniumchloride, trimethylsilylbromoacetate, trimethylsilylchlorosulphonate, 2-(trimethylsilyl)ethoxymethyl chloride, tri(dimethylamino)sulphonium-difluorotrimethylsilicate and 1,3-bis(ch

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