CA1114547A

CA1114547A - Borane reducing resins

Info

Publication number: CA1114547A
Application number: CA291,877A
Authority: CA
Inventors: Larry Manziek
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1976-12-10
Filing date: 1977-11-28
Publication date: 1981-12-15
Also published as: NO784167L; FR2397428A1; DE2755170A1; NO774196L; GB1590548A; IT1093040B; ZA777052B; DE2755170C2; FR2397428B1; SU707524A3

Abstract

ABSTRACT This invention relates to solid nonionic cross-linked resins containing amine or phosphine borane adducts and their use as reducing agents for metal ions, aldehydes, ketones, alkenes and the like. This invention also relates to the use of these resins as starting materials for the preparation of novel metal catalysts for use in hydrogenation reactions.

Description

S~7 Back~round of the Invention It is known in the art, [see M. L. Hal' ensleben, J. PolYmer Science: Symposium No. 47, 1-9 (1974)~, that linear and cross-linked copolymers of L~-vinylpyridine borane, ~-vinylpyridine, and styrene can be prepared and used as poly-meric reducing agents for aldehydes and ketones. It is also reported in the literature~ [see E. Cernia and F. &asparini, J. Applied Polymer Science, vol. 19, 917-20 (1975)], that ~-vinylpyridine borane hydride polymers rapidly decompose in aqueous solutions of strong mineral acids and can only be used as reducing agents for aldehydes and ketones at or about neutral pH. ;
U.S. patent 3,928,293 granted December 23, 1975 discloses solid cross-linked thiohydrocarbon borane hydride -~
polymers and their use as reducing agents for aldehydes ketones, lactones, oxides, esters, carboxylic acids, nitriles and olefins. These borane polymers although stabile at room ;~
temPerature can release borane (BH3) under conditions of reduced pressure or heat and are disclosed as being useful as ;
a convenient means of storing borane. U.S. patent 3,609,191 granted September 28, 1971 discloses polyethylene imine borane complexes which are stable toward hydrolysis at a pH as low as 5Ø These composi tions are use~ul as reducing agents in chemical plating baths for nickel, copper and silver in a pH
range of 5 to 8. However, these products are viscous or solid polymers which range in water solubility from completely soluble to slightly soluble depending on the ratio of BH3 to amino groups in the polymer. The use of in-exchange resins to extract heavy metals from aqueous solutionsvia ion-exchange mechanisms is also reported in the art.

B

1~L14~7 , This invention, in its broadest product aspect, resides in a nonionic borane reducing resin which comprises a solid, cross-linked copolymer containing a plurality of amine-or phosphine-borane adducts.
This invention, more particularly resides in novel solid nonionic borane reducing resins which comprise cross- l linked copolymers containing amine- or phosphine-borane ~:
adducts of the formula ~ 1 . :. ' ~'H 7 Q ~ 3 ~ ~2 (I) .
wherein Q is a group of the formula ~ tCH2)m-T- (CH2)n wherein m and n are independently integers from¦ :
0 to 3; o and T is the group ~ or -CNH-; and ~1 and R2 are independently a) hydrogen;
b) (Cl-C8) optionally substituted alkyl; : :
c) tC6-C12) optionally substituted aryl;
and d) tC7-C12) optionally substituted aralkyl;
and Z is nitrogen or phosphorus, and their use as highly selective reducing agents and as starting materials :~
for the preparation of novel metal catalysts for use in hydrogenation reactions.
The term "alkyl" as utilized in the present speci- . ~.
ficat-on and claims is meant to include both straight and branch chained alkyl groups which can be optionally substi-tuted with up to three substituents, preferably with up to two substituents, more preferably with up to one substituent, B _3_ selected from the group consis-ting of hydroxy, mercapto, fluoro, chloro, bromo, iodo, nitro, methoxy, ethoxy, isopropoxy, amino, methylamino, dimethylamino, ethylamino, diethylamino, amido, methylamido and dimethylamido. `
The term "aryl" as utilized in the present specifi-cation and claims is meant to include aryl groups such as ;~
phenyl, naphthyl and biphenyl, which can be optionally substitut~ `~
with up to three substituents, preferably with up to two substituents~ more preferably with up to one substituent, ~.-selected from the group consisting of fluoro, chloro, bro~o, ;.
iodo, nitro, methyl~ ethyl, methoxy, ethoxy and trihalomethyl.
The term "aralkyl" as utilized in the present speci-fication and claims is meant to include such aralkyl groups as benzyl, phenethyl, phenylpropyl, naphthylmethyl and naphthyl- :-ethyl which can be optionally substituted with up to three .
substituents, preferably with up to two substituents, more .
preferably with up to one substituent, selected from the group consisting of fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, methoxy, ethoxy and trihalomethyl.
The preferred nonionic borane resins of this invention ;
are those wherein T is the group O
-CN~
Z is nitrogen; and Rl and R2 are independently hydrogen, (Cl-C8) unsubstituted alkyl, (C6-C12) unsubstituted aryl or (C7-C12) :
unsubstituted aralkyl.
The more preferred nonionic borane resins of this invention are tnose where T is the group O
-CN~,-;
Z is nitrogen; and Rl and R2 are independently hydrogen, (Cl-C4) unsubstituted alkyl or unsubstituted phenyl, biphenyl, benzyl or phenethyl.
Detailed Descri~tion of the Invention The solid non~ionic cross-linked borane reducing resins of this invention are highly selective reducing agents which are particularly useful in selectively reducing at room temperature, from both aqueous and non-aqueous media, mercury~ silver~ gold~ platinum, palladium, rn~iu~ iridiu~, antimony, arsenic and bismuth ions; to the exclusion of copper, nickel, zinc~ iron, lead, tin~ cadmium, vanadium, chromium, uranium~ thorium, cobalt~ thallium, aluminum and the Group I
and II members of the Periodic Table. These r-sins reduce the metal ions in solution via electron transfer and precipitate the reduced metals on and/or into the resin.
These borane resins are capable of being utilized 1~ over a wide range of pH conditions and can be utilized at pH
ranges greater than about 1.0 but less than about 8Ø These resins are preferably utilized at pH ranges of from about 2.0 to about 4 0 These borane resins are not only stable in aci~
ic and basic media but are also air stable as well.
The solid nonionic cross-linked borane reducing res-ins can also be utilized as reducing agents for aldehydes, ketones, olefins and other functional groups capable of under-going hydroboration reactions. These reagents reduce the aldehydes~ ketones~ olefins and the like via hydride transfer and the resultant product can be liberated from the resin via strong acid hydrolysis. An added eature of this reduction procedure is the ability of these resins to concentrate the products onto the resin thereb~ effecting a concentration and a purification of the products formed before hydrolyzing them off the resin. Although the macroreticular form of the resin , ~ 7 ~:

is preferred, the gel form or any other particulate form of the nonionic borane reducing resins of the present invention can be utilized as reducing agents.
The reduced metals which are precipitated on and/or into the nonioni~c borane reducing resins of the present inven-tion can be either dissolved out of the resin via strong acid or in the case of mercury can be withdrawn by treatment with hot water. The more preferred method of obtaining the reduced precious metals from the resins is by burning the resin away from the metals since the value of the precious metals far exceeds the cost of the resin.
These nonionic borane reducing resins have an advantage over ion exchange resins in that ion exchange resins have distinct leakage problems due to the various ion exchange e~uilibra for each specific metal ion and ion exchanger. There is no such leakage problem due to ion exchange e~uilibrium kinetics in the nonionic borane reducing resins of the present invention. These resins reduce the metals to their zero oxidation state and precipitate them on and/or into the resin.
Another advantage of these resins and in particular of the macro-reticular resins is their ability to contain large capacities ~ -of reduced metals before breakthrough finally occurs.
A preferred embodiment of this invention is the use `
of the solid nonionic cross-linked amine and phosphine borane reducing resins as starting materials for the preparation of novel metal catalysts for use in hydrogenation reactions. The resultant métal containing resins can either be pyrolyzed to give a carbon-metal reduction catalyst or they can be com-busted in the presence of oxygen to give the metal in a bead ' .~

~ -6-., , ., , ~, , ., . . ~ , form. Moreover, catalysts containing known precentages of metals or of mixed metals can be formed via this process.
The nonionic borane reducing resins of the present invention can be prepared by the following general synthetic routes.
In the preparation of the nonionic borane reduclng `
resins of the present invention a suitable water insoluble cross-linked resin having a functional group of the formula ~H Rl ..
~ Rl (II) wherein Q~ Rl, R2 and Z are as defined in Formula (I) above is reacted with a suitable protonating mineral acid such as hydrohalic, phosphoric,sulfuric and the like, preferably B hydrochloric acidJto form the cationic group of the formula ~H2 Rl ~ ~, i`
~H Q____Z-H +

~ ~ R (III) This reaction is carried out in either a batch or column pro- ;~
cess at temperatures from about 0 to about 100C~ preferably at about 200C, in a suitable protic solvent~preferably water.
The amount of protonating acid used can be anywhere from 5%
of the equivalents of weak base in the resin to any percentage over and above the equivalents of weak base in the resin, but is preferably utilized in a 25% excess over the equivalents of weak base in the resin. After the protonation step has taken place the resin is then treated with a water wash to remove any excess acid and then washed thoroughly with a suitable :

.

drying so]vent such as methanol~ éthanol, propanol, acetone, dimethylformamide and the like or alternatively can be air or vacuum dried. In a more preferred process for this protonation step the reaction is carried out in a batch pro-cess and a stoichiometric amount of acid is added to protonate all the available protonizable groups Longer re-action times are preferred in this process since it allows complete diffusion of the acid throughout the resin beads.
- The borane is preferably incorporated into the protonated resin by treating the resin either in a column or batch pro-cess with an excess of a solution of lithium, sodium or potassium borohydride dissolved in an appropriate solvent such as methanol, ethanol, dimethylformamide, monoglyme, diglyme ; and the like at temperatures from about 0 to about 150oC pref-erably at about room temperature.
.... - :
Another method for incorporating the borane into the resin is by directly treating the amine or phosphine function-ality with diborane gas either in a column or batch process or with a solution of diborane in an appropriate solvent such as die'hyl ether~ tetrahydrofuran~ and the like at . ,:. . . ~
temperatures from about 0 to about 150C pre~erably at about room temperature. ;~
.
Those resins which contain amide functions either in the T, Rl, or R2 groups can be converted into amines via ; 25 the use of excess borohydride reagent thereby reducing the bulk and increasing the ratio of the amount of borane to the ` amount of resin.
In the preparations where less than an equivalent of borohydride or diborane is utilized a mixed cationic and ~ 30 nonionic borane reducing agent is obtained which would remove :' ' ~ -8-.. ~.~

metal complex anions and metal cations by both anionic exchange and by reduction of the metal cation or metal complex ;
anion by the borane to the zero oxidation state~
Suitable cross-linked resins which can be utilized in the preparation of the nonionic borane reducing resins of this invention are those described in U,S. patent 2,675,359 granted April ~3, 1974; U. S. patent 3 ,037 ,052 granted May 29, 1962; U. S. patent 3, 531 ,463 granted September 29, 1970; and :
U.S. patent 3,663,467 granted May 16, 1972. These patents may be referred to for suitable procedures for making the corss-linked resins in both the gel and macroreticular form .
described therein. ~ -The following examples are provided to illustrate the preparation of the nonionic borane reducing resins of the ~ -present invention and are not to be considered in any way as limitations on the breadth and scope thereof.

':' -- .

EXAMPLE
Synthesis of the acrylic based amine-borane reducing resin ~
Step A. Protonation -A sample (50.0g) of an acrylic based, macroreticular, 5 weak base resin having a weak base capacity o 5.4 meq. of weak base per gram of dry resin is stirred with an aqueous hydrochloric acid solution containing 360 meq. of hydro- ~-chloric acid (30% excess) for 5 hours. The resin is washed with deionized water to a neutral pH, then with two 300 ml ~ -10 portions of acetone and then vacuum dried at 50C for 8 hours.
Yield, 59.9 grams.
Step B. Borane Addition To a 500 ml round bottom three neck flask equipped ;~ with a sealed mechanical stirrer, pressure compensating 15 dxopping funnel and mineral oil bubbler, is added a sample (52.8g, 238.1 meq. of H+) of a dried acrylic based, macro- -~
reticular weak base resin (in the hydrochloride form) containing 4.51 meq. of H+ per gram of dry resin. A solution of sodium borohydride (10.0 g, 97% purity, 256 meq., 7% excess) in 20 250 ml of dry N,N-dimethylformamide is added rapidly with continuous stirring. The mixture is stirred at room temperature until no further hydrogen gas evolution is observed. The N,~ dimethyl~
formamide is removed by filtration and the remaining resin is backwashed with deionized water until no chloride ion is 25 detectable with silver nitrate and the pH is approximately seven.
The resin is then vacuum dried at 30C. - -Example II

Synthesis of the polystyrene based amine-borane reducing resin.
,.

.

~.
.. . . . . .. ... . .

Step A. Pro'tonat'i'on Utilizing the procedure in Example I Step A ;

and a polystyrene based, macroreticular, weak base `-resin the desired intermediate protonated product is obtained.
'Step B. Borane''Addition ' Utilizing the procedure in Example I Step B and a protonate polystyrene based, macroreticular, weak base resin the desired borane addition product is obtained. ;;
''Ex'a'mple I'II

Synthesis of polystyryl-diphenylphosphine-borane reducing- ~
resin' - - .. - ' Step A. Preparatio'n of pclystyryl-diphenylphosphine ~r Utilizing the procedures in J. Org. Chem. Vol. ~' 40, No. 11, p. 1669 (1975) the macroreticular form of the polystyryl-diphenylphosphine is prépared. ' ' ' Step''B'.' Borane''A'ddi't'ion ,.
A sample of macroretlcular polystyryl-diphenyl- '~' phosphine (lO.Og., 5.0 meq phosphine/gram) is allowed to react with a tetrahydrofuran solution containing diborane (100 ml, 50 meq. BH3). The mixture is stirred at room temperature for 3 hours. The resulting resin is washed with tetrahydrofuran and is vacuum dried.
Example IV ' ., .
Iodine Determination of Borane Concentration in Borane ~ducing Resins The presence and amount of borane functionality is determined by the reaction of the resin with an aqueous iodine solution and titration of excess iodlne with a -standardized solution of sodium thiosulfate. In this ` determination it is imperative that the amount of iodine : -~
--11-- .
~3 ' adsorbed by the resin matrix be calculated for the blank.
Thus, the amount of iodine reduce'd by the borane function-ality is equal to the total amount of iodine removed minus the amo`unt adsorbed by the polymer. This adsorption blank approach is only valid for borane resins containing borane concentrations approaching the theoretical amount7i.e. all ~2 .
weak base sites coordinated wlth borane.
' Examp'l'e ~
Reduction of Cyclohexanone to cyclohexanol with amine~
borane resin in aqueous or' non-aqueous medi'a ~' -Samples of acrylic amine-borane and styrene based amine borane resins as well as their weak base analogs -', from which they are derived are exposed to both aqueous and ;
tetrahydrofuran solutions of cyclohexanone of known con-centration (4%) for a period of two hours. During this time no reaction of the cyclohexanone is observed as evi- ;
denced by a chromatographic determination of its original - concentratlon. To each sample is added an amount of acid, ,~ ;
HCl for the aqueous system and BF3 for the tetrahydrofuran; '' in an amount equivalent to the concentration of the cyclo-hexanone; Both amine-borane resins revealed an immediate decrease in the concentration of cyclohexanone. The for- , mation of cyclohexanol is observed in the aqueous system.
However, no cyclohexanol is observed in the tetrahydrofuran solution which is to be expected in the presence of BF3 -'' which would complex the alcohol. The loss of cyclohexanone is however indicative of the reaction of the amine borane resin with cyclohexanone.

' Ex'ample VI
Batch,equilibrium capacities for several precious metals Batch equilibrium capacities are determined by reacting a known amount of amine-borane resin with an aqueous solution of the metal ion under investigation for a period of 16 hours with continuous shaking. The initial and final concentrations of the metal ion are determined by atomic absorption spectroscopy and capacities calculated from the difference. "
Samples of amine-borane resin are reacted with aqueous solutlons of AuC14- PdC14 , and PtCl-62 of known concentration according to the above procedure. The results ~ ' are listed in the following tabl'e.
Amlne-borane Initial Final resin weightConc. Conc. Capacity '~
in' grams'Metal ion grams' ''grams g metal/gram 0.1090AuC14 0.315 0.0705 2.25 ,, 0.1020PtC16-2 0.322 0.122 1.96 ' 0.1020PdC14-2 0.194 o. 076 1.16 Example ~II
Precious metal recovery by combustion ;
Recovery of the metal from the metal filled beads ls easily accomplished by burning the resin matrix away under an oxygen atmosphere.
A sample of gold filled resin (3.004 g) is combusted at 800C for 30 minutes in a furnace. Bright ' colored metallicgold beads are recovered (1.646g) corres-ponding to an lnltial weight percent of 55%. The beads appear as uniform spheres possessing rough surfaces. Sim-ilar results are obtained from palladium and platinum filled resins under identical conditions.

,. . - i I
.

~4~

'E'x'amp'l'e ~III
Catalyst format'i'ons Samples (l.OOg) of palladium or platinum filled , beads are pyrolyzed at 600C under a stream o~ nitrogen for 30 mins. The resulting spherical beads appear as carbon spheres of high density attributed to the presence -~
of the metal.
' Ex'a'm~'le IX
Metal redu'cing s'elec'tivi't'y The amine-borane resin reactivity for various , -metals is determined by placing a sample (O.lOg) in a vial '~
and adding a concentrated solution of the metal ion or complex under investigation. The vial is allowed to stand for 3 weeks to ensure sufficient contact time. Reaction ,~
is confirmed by either a visible change in the beads such ;
as a darkening in color, an increase in weight of the , , beads when washed with DI water and vacuum-dried, or ' thelr inability to further reduce solutions o~ AuC14-. Like-wlse a positive reduction of AuC14- indicates that no ~eaction.with the metai ion under investigation has occured.
The following table represents those metals investigated and their ability to be reduced.
Metal_Ion Source Not Reduced Reduced Na NaCl ~ _ 25 K+ KCl ~ _ ; L~+ LiCl ~ _ -Mg MgC12 ca+2 2 ~ _ Cr+3 CrC13 ' 30 Cr~6 ~ K2Cr26 ~ _ ~' -.

Metal Ion Source ''Not''Reduced~educed uo2+ 02N3 ~/ '' Bi~3 Bi(NO3)3 . As+3 AS23 Mn~ 2 MnC12 Fe+2 FeC12 ~ _ Fe+3 . 13 ~ ' ' co+2 CoC12 Nl+2 NiC]-2 ~/ _ ''.
cu+2 CuC12 zn+2 ZnC12 ~ _ S~' Rh+3 3 ~ ~ '' pd+2 PdC12 _ 1/ -Ag+l AgNO3 cd+2 CdC12 ~/
Ir+3 IrC13 - J
Pt+4 H2PtC16 Au+3 HAuC14 _ ~ -Hg+2 HgC12 Sb+3 Sb23 -Sr+2 SrC12 / _ pb+2 PbC12 Tl+l T12(S04) ~ _ Pb+4 Et4Pb ~ _ ,, ,~, ?5 CH3Hg CH3HgCl Ex'ample X .
- ' Analy't'l'c'al'det'e'r'mination o'f gold A gold solution containing 5 ppm Au+3 (1000 ml) is allowed to react with a sample of the amine-borane resin 1~4~7 in a column operation under very ~low flows (0.5 ml/min).
Arter loading is completed the resin is assayed for gold and it was determined that a quantitati~-e amount of gold is present; thus, establishing the resin~sut;ility as an analytical method for determining trace amounts of gold or other reactive trace metals. ~
The non-ionic borane reducing resins of this ~' -invention can be utilized in either batch or column oper-ations and in addition to their use as reducing agents for , ', lO metals, aldehydes, ketones and olefins can also be utilized , ~-as an analytical reagent. These resins can be used to de- ''~
tect microquantities of metal ions in various aqueous and '~ ', non-aqueous media due to their ability to quantitatively ~,- .
convert the metal ions to their zero oxidation state and ',~' concentrate the metal on and/or into the resin. The amount metal present in the resultant metal containing resin ', can then be determined via gravimetric, spectroscopic or "
other analytical method and the microquantities of metal in ' the original volume of aqueous or non-aqueous media so treated can then be determined. ' ' The ability of these resins to reduce ionic mercury ' '-salts and compounds and in particular methylmercury makes ,' ', them especially useful in the detoxification of mercury polluted ef~luents.
Another area of application of the non-ionic' ~' borane reducing resins of the present invention is their use ~ ~
ln the sugar refining industry as a decolorizing agent. In I ,;
, similar fashion these resins can be utilized as reducing ~, agents for the' removal of oxide 'impuritles in chemicals such as alcohols, glycols, amines, amides and the like.
:.
` -16-", l :
, I i .

.. ......... . . .- - ~

- 1$g45~7 .
,;~.
These reducing resins can also be utilized for ~-reducing peroxides in peroxide forming organic compounds especially in ethers such as diethylether, tetrahydrofuran, ~-diisopropyl ether and the like. These resins can be utilized , , in the removal of peroxides in ethers already contaminated with perioxides as well as being utilized as peroxide inhib-itors in the storage or use of peroxide forming compounds.
The resins of this inventlon when impregnated with ` ~-metals such as silver, copper, mercury, etc. can be employed -in industrial applications as microbiocides in the textiles, paint, paper and laundry industries. These same resins can also find application in the removal of trace amounts of hydrogen sulfide, sulfur dioxide and the like from natural `
gas streams, coal gasification streams, coal and oil burning :
utility plants, sulfuric acid plants and the like. In these latter applications the potential high surface area of the finely divided, supported metal provides a high capacity material. The non-ionic borane reducing resins can also be utilized in elemental halogen and alkyl halide removal from aqueous and non-aqueous medla via reduction to halide ion and an alkane respectively. ~`
. .
; Certain of the non-ionic amine-borane reducing resins of this invention have applicability in organic synthesis procedures since the borane-resin adduct provides the desir-able features that the reducing support is easily removed ~ `
from the reaction mixture, the reduced material is attached to the resin system providing for complete separation of the product from the starting material. The reduced material can then be recovered from the resin by acid or base hydroly- ;-sis providing a pure product. The reducing support can then -... ' ' _17-. . . ~ . ~ ,, r r ~., 1~ 7 be chemically regenerated to the starting non-ionic amine borane reducing resin by procedures outlined above.
Another advantage of the borane reducing resins of -this invention is their ability to provide a source of borane without the hazards associated with the use of this reagent. Another application for the amine-borane resins of the presént invention is their use in the petroleum ' .' ` "?
industry. Petroleum refining plants utilize noble metals as catalysts. These metals are presently recovered by dissol-ving them in aqua regia and then chemically reducing the , ~ -metal chloride salts. However, the effluent from this process still contains about 10 to 15 ppm of metal ionO
Anion exchange resins are presently used to remove these final trace amounts of metal. However, rhodium salts are not efficiently removed by anion exchange resins. Thus, - ~`
the use of the high capacity amine-borane resins of the present invention can be used in place of the anion exchange resins in the above recovery process. The nonionic cross-linked resins containing amine or phosphine borane adducts can ~;
be advantageously employed in numerous applications as disclosed above. Other applications of these adducts which -readily suggest themselves to those skilled in the art are meant to be included within the scope of the present speci-fication and claims.

- . . - .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A nonionic borane reducing resin which com-prises a solid, cross-linked copolymer containing a plurality of amine-or phosphine-borane adducts.

2. A resin according to claim 1 wherein the amine-or phosphine-borane adducts are of the formula wherein Q is a group of the formula -(CH2)m-T-(CH2)-n wherein m and n are independently integers from 0 to 3; and T is the group or ; and R1 and R2 are independently a) hydrogen;
b) (C1-C8) alkyl optionally substituted with from 1 to 3 substituents selected from the group consisting of hydroxy, mercapto, fluoro, chloro, bromo, iodo, nitro, methoxy, ethoxy, isopropoxy, amino, methylamino, dimethylamino, ethylamino, diethyleamino, amido, methlamido and dimethylamido;
c) (C6-C12) aryl optionally substituted with from 1 to 3 substituents selected from the group consisting of fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, methoxy, ethoxy and trihalomethyl;

d) (C7-C12) aralkyl optionally substituted with from 1 to 3 substituents selected from the group consisting of fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, methoxy, ethoxy and trihalomethyl; and Z is nitrogen or phosphorus.

3. A resin according to claim 2 wherein R1 and R2 are independently hydrogen, (C1-C8) unsubstituted alkyl, (C6-C12) unsubstituted aryl or (C7-C12) unsubstituted aralkyl.

4. A resin according to claim 3 wherein T is the group and Z is nitrogen.

5. A resin according to claim 4 wherein R1 and R2 are independently hydrogen, (C1-C4) unsubstituted alkyl or unsubstituted phenyl, biphenyl, benzyl or phenethyl.

6. A resin according to claim 5 wherein said resin is in a macroreticular form.

7. A process for the reduction of aldehydes, ketones and olefins which comprises contacting an aldehyde, ketone or olefin with a resin according to claim 1, hydrolyzing the reduced product off the resin, and isolating the reduced product.