27  5,744,649  28  IDustrative  optically  active  or  prochiral  olefinic  com› pounds  useful  in  asymmetric  hydroformylation  include,  for  example,  p-isobutylstyrene,  2-vinyl-6-methoxy-2- naphthylene,  3-ethenylphenyl  phenyl  ketone,  4-ethenylphenyl-2-thie  nylketone,  4-ethenyl-2- fluorobiphenyl.  $_{4-( }$l.3-dihydro-1-oxo-2H-isoindol-2-yl)  styrene.  2-ethenyl-5-benzoylthiophene.  3-ethenylphenyl  phenyl  ether.  propenylbenzene,  isobutyl-4- propenylbenzene,  phenyl  vinyl  ether  and  the  like.  Other  olefinic  compounds  include  substituted  aryl  ethylenes  as  Most  preferably  the  subject  invention  is  especially  useful  for  the  production  of  non-optically  active  aldehydes,  by  hydroformylating  achiral  alpha-olefins  containing  from  2  to  30.  preferably  4  to  20.  carbon  atoms,  and  achiral  internal  olefins  containing  from  4  to  20  carbon  atoms  as  well  as  starting  material  mixtures  of  such  alpha  olefins  and  internal  olefins.  The  substituted  or  unsubstituted  olefinic  unsaturated  start- ing  material  reactants  that  may  be  employed  in  the  hydro› formylation  processes  of  this  invention  include  both  opti› cally  active  (prochiral  and  chiral)  and  non-optically  active  (achiral)  olefinic  unsaturated  compounds  containing  from  2  to  40,  preferably  4  to  20,  carbon  atoms.  Such  olefinic  unsaturated  compounds  can  be  terminally  or  internally  unsaturated  and  be  of  straight-chain,  branched  chain  or  cyclic  structures,  as  well  as  olefin  mixtures.  such  as  obtained  from  the  oligomerization  of  propene,  butene,  isobutene,  etc.  (such  as  so  called  dimeric,  trimeric  or  tetrameric  propylene  and  the  like,  as  disclosed,  for  example,  in  U.S.  Pat.  Nos.  4.518,809  and  4.528,403).  Moreover,  such  olefin  com› pounds  may  further  contain  one  or  more  ethylenic  unsatur› ated  groups,  and  of  course,  mixtures  of  two  or  more  different  olefinic  unsaturated  compounds  may  be  employed  as  the  starting  hydroformylation  material  if  desired.  For  example,  commercial  alpha  olefins  containing  four  or  more  carbon  atoms  may  contain  minor  amounts  of  corresponding  internal  olefins  and/or  their  corresponding  saturated  hydrocarbon  and  that  such  commercial  olefins  need  not  necessarily  be  purified  from  same  prior  to  being  hydroformylated.  mustra› tive  mixtures  of  olefinic  starting  materials  that  can  be  employed  in  the  hydroformylation  reactions  include,  for  example.  mixed  butenes.  e.g.,  Raffinate  I  and  II.  Further  such  olefinic  unsaturated  compounds  and  the  corresponding  aide- hyde  products  derived  therefrom  may  also  contain  one  or  more  groups  or  substituents  which  do  not  unduly  adversely  affect  the  hydroformylation  process  or  the  process  of  this  invention  such  as  described,  for  example,  in  U.S.  Pat.  Nos.  3.527  ,809.  4,769.498  and  the  like.  wherein  R$_{1}$ ,  R$_{2}$ •  R$_{3 }$ and  R$_{4 }$ are  the  same  or  different  (provided  R $_{1 }$ is  different  from  R$_{2 }$ or  R$_{3 }$ is  different  from  ~)  and  are  selected  from  hydrogen;  alkyl;  substituted  alkyl,  said  substitution  being  selected  from  dialkylamino  such  as  ben› zy  lamino  and  dibenzylamino,  alkoxy  such  as  methoxy  and  ethoxy.  acyloxy  such  as  acetoxy.  halo,  nitro,  nitrile,  thio,  carbonyl,  carboxamide,  carboxaldehyde.  carboxyl.  carboxy- lic  ester;  aryl  including  phenyl;  substituted  aryl  including  phenyl.  said  substitution  being  selected  from  alkyl.  amino  including  alkylamino  and  dialkylarnino  such  as  benzy› lamino  and  dibenzylamino,  hydroxy,  alkoxy  such  as  meth› oxy  and  ethoxy.  acyloxy  such  as  acetoxy,  halo,  nitrile,  nitro,  carboxyl,  carboxaldehyde,  carboxylic  ester,  carbonyl,  and  thio;  acyloxy  such  as  acetoxy;  alkoxy  such  as  methoxy  and  ethoxy;  amino  including  alkylarnino  and  dialkylamino  such  as  benzylamino  and  dibenzylarnino;  acylamino  and  diacy› larnino  such  $_{as }$acetylbenzylamino  and  diacetylamino;  nitro;  carbonyl;  nitrile;  carboxyl;  carboxamide;  carboxaldehyde;  carboxylic  ester;  and  alkylm.ercapto  such  as  methylmer› capto.  It  is  understood  that  the  prochiral  and  chiral  olefins  of  this  definition  also  include  molecules  of  the  above  general  formula  where  the  R  groups  are  connected  to  form  ring  compounds.  e.g  .•  3-m.ethyl-1-cyclohexene.  and  the  like.  (XII)  Prochiral  and  chiral  olefins  useful  in  the  asymmetric  hydroformylation  that  can  be  employed  to  produce  enantio› meric  aldehyde  mixtures  that  may  be  encompassed  by  in  this  invention  include  those  represented  by  the  formula:  More  preferably.  the  reaction  is  carried  out  in  the  slurry  phase  due  to  the  high  boiling  points  of  the  products,  and  to  avoid  decomposition  of  the  product  aldehydes.  The  catalyst  may  then  be  separated  from  the  product  mixture,  for  example.  by  filtration  or  decantation.  The  reaction  product  fluid  may  contain  a  heterogeneous  metal-organophosphite  ligand  complex  catalyst.  e.g.,  slurry,  or  at  least  a  portion  of  the  reaction  product  fluid  may  contact  a  fixed  heterogeneous  metal-organophosphite  ligand  complex  catalyst  during  the  hydroformylation  process.  In  an  embodiment  of  this  invention,  $_{the }$metal-organophosphite  ligand  complex  cata› lyst  may  be  slurried  in  the  reaction  product  fluid.  Illustrative  alpha  and  internal  olefins  include,  for  example,  ethylene,  propylene,  1-butene,  1-pentene,  1-hexene.  1-octene,  1-nonene,  1-decene,  1-undecene,  1-dodecene.  1-tridecene.  1-tetradecene.  1-pentadecene,  1-hexadecene.  1-heptadecene.  1-octadecene,  1-nonadecene.  1-eicosene.  2-butene,  2-methyl  propene  (isobutylene),  2-methylbutene,  2-pentene.  2-hexene.  3-hexane,  2-heptene.  2-octene,  cyclohexene,  propylene  dimers,  propylene  trimers,  propylene  tetramers,  butadiene,  piperylene,  isoprene,  2-ethyl-1-hexene,  styrene,  4-methyl  styrene.  4-isopropyl  styrene.  4-tert-butyl  styrene.  alphamethyl  styrene,  4-tert› butyl-alpha-methyl  styrene,  1.3-diisopropenylbenzene,  3-phenyl-1-propene.  1,4-hexadiene,  1.7-octadiene,  3-cyclohexyl-1-butene,  and  the  like.  as  well  as.  1.3-dienes,  butadiene,  alkyl  alkenoates.  e.g.,  methyl  pentenoate.  alkenyl  alkanoates,  alkenyl  alkyl  ethers,  alkenols,  e.g.,  pentenols,  alkenals,  e.g.,  pentenals,  and  the  like,  such  as  allyl  alcohol,  allyl  butyrate,  hex-1-en-4-ol,  oct-1-en-4-ol.  vinyl  acetate,  allyl  acetate,  3-butenyl  acetate.  vinyl  propionate,  allyl  propionate,  methyl  methacrylate,  vinyl  ethyl  ether,  vinyl  methyl  ether,  allyl  ethyl  ether,  n-propyl-7-octenoate,  3-butenenitrile.  5-hexenamide,  eugenol.  iso-eugenol,  safrole.  iso-safrole,  anethol,  4-allylanisole,  indene,  limonene,  beta-pinene,  dicyclopentadiene,  cyclooctadiene,  camphene,  linalool.  and  the  like.  In  the  heterogeneous  catalysts  described  above,  the  cata› lyst  may  remain  in  its  heterogeneous  form  during  the  entire  hydroformylation  and  catalyst  separation  process.  In  another  embodiment  of  the  invention,  the  catalyst  may  be  supported  on  a  polymer  which.  by  the  nature  of  its  molecular  weight.  is  soluble  in  the  reaction  medium  at  elevated  temperatures,  but  precipitates  upon  cooling,  thus  facilitating  catalyst  sepa› ration  from  the  reaction  mixture.  Such  "soluble"  polymer› supported  catalysts  are  described  in  for  example:  Polymer,  1992.  33.  161;  J.  Org.  Chem.  1989,  54,  2726-2730.  containing  ligand.  such  as  a  phosphite,  incorporated  into  the  polymer.  The  supported  catalyst  is  not  limited  by  the  choice  of  polymer  $_{or }$phosphorus-containing  species  incorporated  into  it.  Descriptions  $_{of }$polymer-supported  catalysts  may  be  found  in  for  example:  J.  Mol.  Cat.  1993,  83.  17-35;  Chemtech  1983,  46;  J.  Am.  Chem.  Soc.  1987.  109,  7122-7127. 