CA1114401A - Selective oxoamination process - Google Patents
Selective oxoamination processInfo
- Publication number
- CA1114401A CA1114401A CA297,954A CA297954A CA1114401A CA 1114401 A CA1114401 A CA 1114401A CA 297954 A CA297954 A CA 297954A CA 1114401 A CA1114401 A CA 1114401A
- Authority
- CA
- Canada
- Prior art keywords
- ptc12
- snc12
- linear alkyl
- aldehyde
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
SELECTIVE OXOAMINATION PROCESS
(73,915 -F) ABSTRACT OF THE INVENTION
This invention concerns the synthesis of linear alkyl primary amines from .alpha.-olefins via an oxoamination process comprising (a) hydrogen and carbon monoxide addi-tion to olefinic substrates to obtain aldehyde-containing compounds in the presence of ligand-stabilized platinum(II) halide catalysts with Group IVB metal halide cocatalysts, and (b) reductive amination of said aldehydic intermediates in the presence of oxide-supported, nickel catalysts.
I
(73,915 -F) ABSTRACT OF THE INVENTION
This invention concerns the synthesis of linear alkyl primary amines from .alpha.-olefins via an oxoamination process comprising (a) hydrogen and carbon monoxide addi-tion to olefinic substrates to obtain aldehyde-containing compounds in the presence of ligand-stabilized platinum(II) halide catalysts with Group IVB metal halide cocatalysts, and (b) reductive amination of said aldehydic intermediates in the presence of oxide-supported, nickel catalysts.
I
Description
SI~ARY OF I~YENTION
Thi3 lnven tion concern~ a proce~3 for the oxs~-amination o~ alpha ~a) oleins to lin~ar alkyl primary am~ne~ without the need or i501ating the intermedia~e linear alkyl ald~hydes.
~ ore paæticularly9 ~his in~ention rela~es to ehe ca~calytic sxoam~na ion of a~olefin~ ~o llnear alkyl pr~nary amines usi~g flr~t, a ligand stabil~zed platlnum(II) halide-Group IVB metal halide for the catalytic addi~iorl o hydrogen and carbon morloxide eO said ole~inic sub~t~at~s to obtain linear alk~rl aldehyde3 as i~te~mediat~s~ ~heT~
reduc~ively amlna'c~ng sa~d alk~l aldehydes to ~he d~iqred l~near alk~l amine~ through the addition of ~ydrogen and ammonia in the presence of o~ide-sllpported r~ickel cataly3ts.
~AC~OTIIID 011 ~ I~l 1011 Large qua~l:itles 02e linear alkyl primary a~ines ~re presently produced commercia~ ly fro~ ~he ~atural ~tty acids in coconut oil, palm oil, tal~ow, etc. Th~ ~arl~et for he~e amine~ exceed~ 100 ~IM lbslyr, ~ith applica~ion~
20 irl the rubber and detergerlt industries and as ch~mlc 1 in~ce~nediate~ Thi~ invention concerns the syrlt~esis of linear alkyl primarg ~in~s f~om a petrochemical source, viz, a-oleins, via an oxoamination process~ Said proce~s comprises (a) hydroformyla~ion of linear alkyl a-olefin '` substrates to the corresponding straight~chain aldehydes containing one more car~on atom ~Eq. 1~ and (b) amina~ion of said linear aldehyde to the corresponding desired linear alkyl pr~na~y amir~e (Eq. 2).
~4~
~CH~ 2 ~ t::O t ~I~ ~ R~ Hz-C H2-CHO (1) ~CH2-~12-C~ * ~ ~ H2 _ R~I2~ 2~12 NH2 ~ ~2 (~) Aft~r an ext~n3i~ae re3earc:h program 'che appl~-cants ha~ de-Jeloped a cla~ of lig~md-~ab~li?ed pla~i~um(II)-Group IVB Dletal halide cataly3~s for 3~ep which a~ the adva~tages o~
1) ~Ii~h s~lec~i~ity to ~h~ ~lnear aldehyde i*
seep 1 wi~ch lit~le branched aldehyde contamlnant 23 Ease of ~epara~oo of the interm~dia~e alde~
hydes from the plstin~ catalgst, pRrticularïy in th0 ca~e o di~per3io~ of the ligand-stabilized platinum~II) halide catalyst in quaternary ammoni-~m qalt~ of ~richlvro-stan~ate(lI), without h~ ~eed o deseroy~ or pret ipita~e, th~ cataly~ ~19 in analogousJ cobalt io~O~ technology.
3) Fur'chenno~ aid di~per~ion o~ ligand~
~tabilized platinuD~tII9 hallde catalysts in quat~rnary a~onium salts of trichlorosta~ate (II3 r~main ActiYe af~r l~n~ar aldehyde reeovesy and may be recycled wil:h fre~h c~-ole~in charg~, thereby ac~ieYi~g addit~onal llnear alde-hyde synthese~. ~
The ~las~ o oxide~supported nickel-containing cataly~ts developesl by the applicant3 for step 2, the re-duc~ive aminaeion of the linear aldehydie intermediates to linear alkyl pr.ima~:y amines, also have the intrinsic ~ . .
a~vantages of:
1~ Exhibi.~inæ high ~electivity to said linear alkyl primary ami~e with little fo~ation of branched alkyl or ~econdary amine fo~mation.
snd 2) Good ~peci:ElE act~rits~, which allow~ the reducelve a~iaation reaction eO be carsei~d o~ rapidly under moderate condition~ of temperature and pre~sure.
PRIOR ART
'~ It is ~own ~ che are how to pr~par~ aldehydes fro~a olefinic ~ub~traee~ Ruch a~ e~:hyler~e, propylene sr l~butene u~ing carbon monoxid~ and hydrogen at ele~al:ed t~perature~ arld pre~sur~3. ~ormally the e proce~e~ are catalytic and are conducted in.the presence of homogeneous io or he~esogeneou~ ca~cal~qts (see equatio~s shown above).
Similarly, l~c is kwwn how ~o reducs ~he aldehyde ir~ter-~ediate~ to the corse3ponding ~nines using a gseae Ya~iety of ca~aly~ts~upported (he~rogeneou~) and non-~upporeed (homogeneous). A gyp:lcal ~a~pling of the proce~e~ u~ed to fon~ ehe aldehyde~ from olefln3 (hydroonnylation) include U. S. Patent~ ~5,981,925, :~,657,368 and United ~ingdom 1,138,601. The so~ond stag~ of the overall proce~ that ~s the ~eduction o~ ldehyde~ to as~ e product ~ is broadly ~et foreh in the lltera~ure and speciie pat~n~s will not 2û be ~t . or~h., Elowever~ ehe ~elec~ve reduction o aldehyde i~t n~ediates9 ~uch as have b~ producad by ehe first catalyt~c tra~orma~ion, without the need or i~olatin~
the aldehyde, 1~ believed t~ be novel in the ar~ par~icu-larly when using ~.hese oxide- upported, nic~ containing `~ ca~a lys t9 .
In vi~w of thi~ unusual combination of advantages, ~he inventive process repres~nts an improvement in sub-9 tance in view of the art .
,~ ..
, . .
In ~he b~oadest contemplated practice of ~his i~v~ntion, ~ub tantia~ quanti~ie3 of llnear alkyl primar~y amine~ are produced by ~he oxoamination of alpha olefln ~ubs~ra~es containing 2 ~co 30 carbon a~ by the step of:
a~ fonDiag a hydroformyl.a~ion react~on IDixture of -olefin ~ub~trate9 carboTI mono~id~, ~ydrogen and :Erom a~out 0.001 to 0.1 ~uoles of a ~hre~-componen~ gand-~t~i~ized~ platinum(II3 halld~ ~ataly~t p r mole of ole-fitl 3ubstrate, ~a~d ca~aly~s being 3elected frolD ~he g~oup ~o con~is ting of:
PtCl2~P(CgH5):~] 2~SnC:12 PtC12 ~P (p-C~ Ce~H4 )3 ] 2+Sn~:12 p~ 2 rP (n-C4~ ] 2~SnCiL~2 PtC 12 l~P (~e~H5 ~ 3 ] z~5nc 1~
PtCl2 lP ~ceH5 )g ] 2~GeCl2 PtC 12 ~ P tCH3 ) 2Co~I5 1 2~SnC 12 PtCl2~PhzAsCH2CH2AsPh2~+SnCl2 P~cC 12 t P (ûC~lIs ) 9 3 2 tSnC 12 Pti::latA5 ~C~HS)3~ 2tSnCl2 PtCl2 rs (C~Is ) ~ 2~SnCl2 PtBr2~p(c:o~ls)~2+snBr2 PtCl2 [Ph2PC~12CH2PPh2~ ~Sr~Cl2 PtCl2 [Sb (C~IS)3~ 2~SnCl2 PtC 12 ~o~Phenanthr~line )~SnC l:a Ptcl2~ptcsHs)3]2~cl3sn] L~(C2HS)4]
,~ . . " +[Cl3SnJ [P(C,SHs)3c~I2cl]
[C13Sn ] [~ Hg ) ~ ]
C 19Sn ] EAS (G~H5 ) ~ ]
l~ +~Cl3Sn] [N(C7Hls)~]
~ ~[cl3Ge; E~(C2EI5)~]
Pt~2~p(p~ c~H~)3J 2~[cl3sn] [N(c2~5)~]
Ptcl2Zp(n-c~H9)3]2~cl3sn] ~NtC2EIs343 .. . . . ~ .
the carbon monoxide and hydrogen being present in quantities sufficient to satisfy the stoichiometry of the hydroformyla-tion reaction.
b) pressurizing the hydroformylation reaction mixture between about 100 psig to about 3000 psig and heat-ing the pressurized reaction mixture at about 25C to about 125C until a major amount of linear alkyl aldehyde products and a minor amount of non-linear alkyl aldehyde products are formed, and c) contacting said li.near alkyl aldehyde products with at least sufficient hydrogen and ammonia to satisfy the stoichiometry of reducing th0 linear alkyl aldehyde to linear alkyl primary ami.ne product, pressurizing between about 100 psig to about 3000 psig and heating said linear alkyl alde-hyde from about 25 to about 200C, in the presence of a catalyst consisting essentially of oxide supported nickel catalyst containing from 5% to about 75 weight % nickel until a substantial amount of linear alkyl primary amine product is fo~med, and 20.~ d) isolating the linear alkyl primary amine prod-uct contained therein.
A. PRO~ S~ __E AND VARIATIONS
..
In general, the components of the hydroformyla-tion reaction mixture, including optional inert solvent, olefin and platinum catalyst may be added in any sequence as long as good agitation is employed to provide a good dispersion or a homogeneous reaction mixture. For example, the following represent some variations insofar as the addition of catalyst components, inert solvents and olefin addition that may be made without departing from the ~ ' .
.
,: - ' , . :
inventive p~oce~. The~e modifica~iorls include:
1) The ç:at81y3t may be pr~ormed ~nd added pr~
fo~d ~o the ~eact~on solvent prior to the addition of the olefin and other inert solven1: compo~ent~.
i~ 2) Preferably, to miTIiDlize s~abili~y proble~
wi~h ~he cat Iys~9 ~he ca~ l;y~t ls be~t ormed in ~itu usually by mixing the deo~gea~tecl i~t ~o~ven~ and --. .
~eat olefin, followed by ~he add~tion o~ the ~xce~s m~tal halide o Group IYB, and finally by the addition of the 10 ligand stabi~ized platinur~ complex ~o form the reac-tion mixtur~.
3) ~ter ~asing either Yaria~ion i or 2, the de-oxygenated catalyst containing reactlon ~lxture i~ pre~ur-lzed with C0 and hydrogen and heated until t}ie ldehyd~
pro~uct i8 ~ormad.
~ ) An e3pecially pre~rred modi~ca~:Zon, whieh ~irlimizes both 'che induction period and ~he isomerization of the ol fin, i8 the ollowing: the cata7y~t i~ formed in a deoa:ygena~ed solvent, t7he cal:aly~t qolution ls pre~sur-20 i~t with carbon monoxide and hydro~ser~ and heated to ~hedesired reactiorl temperature; olein i8 then added neat or dissolv~d i~ a ~uitabl~ sol~en~ reActiorl miacture i3 a~itated under C0 an~ ~12 at the da~ d reaction ~emperature un~cil . he aldehycle product i~ formed.
5) A ~cond preferred modif~cation, i~ the use of di~persionq of. ~aid ligand-~tabili~ed platinum(II) halide complexes in low~melting gua~ernary alkyl sal~:s of trl-chlorostannate (II) or trichlorogerma~ate (II~ as catalys~s for the conversio~ of alpha-oleins ~o the corresponding lin~ar alkyl aldehyde.
_6_ - . . . . -, : .
. .
, LtGAND-5T~ ZEI) PIATINUM E~ROFOE?MYLA~ION
C~TAIXSTS
S~me ligand-~abiliz~d.l, platinl~m(II) halide, Group IVB metal halide co~plexe~ are ~own in the litera~
ture and me~hod~ for ~be~r preparation haY~ been de~cribed*.
`-' One conver3ient mode of preparat-lon in ~itu i8 to mix a ~olu-~iorl of plai:inum(II) halide complex ~uch a~ PtCl2[PtC~Hs)3~
with ~ lar~3;e mola~ esc~eqs o~ ~roup IVB metaL halide, pr~er-e~ially SnCl2.
10The three cGmponent ligand-~tabillzed platinum(II) ca~caly~t compos~tion of thi~ ventio~ cor~ t~ e~ntlally 1~ platirlum (II ) halides
Thi3 lnven tion concern~ a proce~3 for the oxs~-amination o~ alpha ~a) oleins to lin~ar alkyl primary am~ne~ without the need or i501ating the intermedia~e linear alkyl ald~hydes.
~ ore paæticularly9 ~his in~ention rela~es to ehe ca~calytic sxoam~na ion of a~olefin~ ~o llnear alkyl pr~nary amines usi~g flr~t, a ligand stabil~zed platlnum(II) halide-Group IVB metal halide for the catalytic addi~iorl o hydrogen and carbon morloxide eO said ole~inic sub~t~at~s to obtain linear alk~rl aldehyde3 as i~te~mediat~s~ ~heT~
reduc~ively amlna'c~ng sa~d alk~l aldehydes to ~he d~iqred l~near alk~l amine~ through the addition of ~ydrogen and ammonia in the presence of o~ide-sllpported r~ickel cataly3ts.
~AC~OTIIID 011 ~ I~l 1011 Large qua~l:itles 02e linear alkyl primary a~ines ~re presently produced commercia~ ly fro~ ~he ~atural ~tty acids in coconut oil, palm oil, tal~ow, etc. Th~ ~arl~et for he~e amine~ exceed~ 100 ~IM lbslyr, ~ith applica~ion~
20 irl the rubber and detergerlt industries and as ch~mlc 1 in~ce~nediate~ Thi~ invention concerns the syrlt~esis of linear alkyl primarg ~in~s f~om a petrochemical source, viz, a-oleins, via an oxoamination process~ Said proce~s comprises (a) hydroformyla~ion of linear alkyl a-olefin '` substrates to the corresponding straight~chain aldehydes containing one more car~on atom ~Eq. 1~ and (b) amina~ion of said linear aldehyde to the corresponding desired linear alkyl pr~na~y amir~e (Eq. 2).
~4~
~CH~ 2 ~ t::O t ~I~ ~ R~ Hz-C H2-CHO (1) ~CH2-~12-C~ * ~ ~ H2 _ R~I2~ 2~12 NH2 ~ ~2 (~) Aft~r an ext~n3i~ae re3earc:h program 'che appl~-cants ha~ de-Jeloped a cla~ of lig~md-~ab~li?ed pla~i~um(II)-Group IVB Dletal halide cataly3~s for 3~ep which a~ the adva~tages o~
1) ~Ii~h s~lec~i~ity to ~h~ ~lnear aldehyde i*
seep 1 wi~ch lit~le branched aldehyde contamlnant 23 Ease of ~epara~oo of the interm~dia~e alde~
hydes from the plstin~ catalgst, pRrticularïy in th0 ca~e o di~per3io~ of the ligand-stabilized platinum~II) halide catalyst in quaternary ammoni-~m qalt~ of ~richlvro-stan~ate(lI), without h~ ~eed o deseroy~ or pret ipita~e, th~ cataly~ ~19 in analogousJ cobalt io~O~ technology.
3) Fur'chenno~ aid di~per~ion o~ ligand~
~tabilized platinuD~tII9 hallde catalysts in quat~rnary a~onium salts of trichlorosta~ate (II3 r~main ActiYe af~r l~n~ar aldehyde reeovesy and may be recycled wil:h fre~h c~-ole~in charg~, thereby ac~ieYi~g addit~onal llnear alde-hyde synthese~. ~
The ~las~ o oxide~supported nickel-containing cataly~ts developesl by the applicant3 for step 2, the re-duc~ive aminaeion of the linear aldehydie intermediates to linear alkyl pr.ima~:y amines, also have the intrinsic ~ . .
a~vantages of:
1~ Exhibi.~inæ high ~electivity to said linear alkyl primary ami~e with little fo~ation of branched alkyl or ~econdary amine fo~mation.
snd 2) Good ~peci:ElE act~rits~, which allow~ the reducelve a~iaation reaction eO be carsei~d o~ rapidly under moderate condition~ of temperature and pre~sure.
PRIOR ART
'~ It is ~own ~ che are how to pr~par~ aldehydes fro~a olefinic ~ub~traee~ Ruch a~ e~:hyler~e, propylene sr l~butene u~ing carbon monoxid~ and hydrogen at ele~al:ed t~perature~ arld pre~sur~3. ~ormally the e proce~e~ are catalytic and are conducted in.the presence of homogeneous io or he~esogeneou~ ca~cal~qts (see equatio~s shown above).
Similarly, l~c is kwwn how ~o reducs ~he aldehyde ir~ter-~ediate~ to the corse3ponding ~nines using a gseae Ya~iety of ca~aly~ts~upported (he~rogeneou~) and non-~upporeed (homogeneous). A gyp:lcal ~a~pling of the proce~e~ u~ed to fon~ ehe aldehyde~ from olefln3 (hydroonnylation) include U. S. Patent~ ~5,981,925, :~,657,368 and United ~ingdom 1,138,601. The so~ond stag~ of the overall proce~ that ~s the ~eduction o~ ldehyde~ to as~ e product ~ is broadly ~et foreh in the lltera~ure and speciie pat~n~s will not 2û be ~t . or~h., Elowever~ ehe ~elec~ve reduction o aldehyde i~t n~ediates9 ~uch as have b~ producad by ehe first catalyt~c tra~orma~ion, without the need or i~olatin~
the aldehyde, 1~ believed t~ be novel in the ar~ par~icu-larly when using ~.hese oxide- upported, nic~ containing `~ ca~a lys t9 .
In vi~w of thi~ unusual combination of advantages, ~he inventive process repres~nts an improvement in sub-9 tance in view of the art .
,~ ..
, . .
In ~he b~oadest contemplated practice of ~his i~v~ntion, ~ub tantia~ quanti~ie3 of llnear alkyl primar~y amine~ are produced by ~he oxoamination of alpha olefln ~ubs~ra~es containing 2 ~co 30 carbon a~ by the step of:
a~ fonDiag a hydroformyl.a~ion react~on IDixture of -olefin ~ub~trate9 carboTI mono~id~, ~ydrogen and :Erom a~out 0.001 to 0.1 ~uoles of a ~hre~-componen~ gand-~t~i~ized~ platinum(II3 halld~ ~ataly~t p r mole of ole-fitl 3ubstrate, ~a~d ca~aly~s being 3elected frolD ~he g~oup ~o con~is ting of:
PtCl2~P(CgH5):~] 2~SnC:12 PtC12 ~P (p-C~ Ce~H4 )3 ] 2+Sn~:12 p~ 2 rP (n-C4~ ] 2~SnCiL~2 PtC 12 l~P (~e~H5 ~ 3 ] z~5nc 1~
PtCl2 lP ~ceH5 )g ] 2~GeCl2 PtC 12 ~ P tCH3 ) 2Co~I5 1 2~SnC 12 PtCl2~PhzAsCH2CH2AsPh2~+SnCl2 P~cC 12 t P (ûC~lIs ) 9 3 2 tSnC 12 Pti::latA5 ~C~HS)3~ 2tSnCl2 PtCl2 rs (C~Is ) ~ 2~SnCl2 PtBr2~p(c:o~ls)~2+snBr2 PtCl2 [Ph2PC~12CH2PPh2~ ~Sr~Cl2 PtCl2 [Sb (C~IS)3~ 2~SnCl2 PtC 12 ~o~Phenanthr~line )~SnC l:a Ptcl2~ptcsHs)3]2~cl3sn] L~(C2HS)4]
,~ . . " +[Cl3SnJ [P(C,SHs)3c~I2cl]
[C13Sn ] [~ Hg ) ~ ]
C 19Sn ] EAS (G~H5 ) ~ ]
l~ +~Cl3Sn] [N(C7Hls)~]
~ ~[cl3Ge; E~(C2EI5)~]
Pt~2~p(p~ c~H~)3J 2~[cl3sn] [N(c2~5)~]
Ptcl2Zp(n-c~H9)3]2~cl3sn] ~NtC2EIs343 .. . . . ~ .
the carbon monoxide and hydrogen being present in quantities sufficient to satisfy the stoichiometry of the hydroformyla-tion reaction.
b) pressurizing the hydroformylation reaction mixture between about 100 psig to about 3000 psig and heat-ing the pressurized reaction mixture at about 25C to about 125C until a major amount of linear alkyl aldehyde products and a minor amount of non-linear alkyl aldehyde products are formed, and c) contacting said li.near alkyl aldehyde products with at least sufficient hydrogen and ammonia to satisfy the stoichiometry of reducing th0 linear alkyl aldehyde to linear alkyl primary ami.ne product, pressurizing between about 100 psig to about 3000 psig and heating said linear alkyl alde-hyde from about 25 to about 200C, in the presence of a catalyst consisting essentially of oxide supported nickel catalyst containing from 5% to about 75 weight % nickel until a substantial amount of linear alkyl primary amine product is fo~med, and 20.~ d) isolating the linear alkyl primary amine prod-uct contained therein.
A. PRO~ S~ __E AND VARIATIONS
..
In general, the components of the hydroformyla-tion reaction mixture, including optional inert solvent, olefin and platinum catalyst may be added in any sequence as long as good agitation is employed to provide a good dispersion or a homogeneous reaction mixture. For example, the following represent some variations insofar as the addition of catalyst components, inert solvents and olefin addition that may be made without departing from the ~ ' .
.
,: - ' , . :
inventive p~oce~. The~e modifica~iorls include:
1) The ç:at81y3t may be pr~ormed ~nd added pr~
fo~d ~o the ~eact~on solvent prior to the addition of the olefin and other inert solven1: compo~ent~.
i~ 2) Preferably, to miTIiDlize s~abili~y proble~
wi~h ~he cat Iys~9 ~he ca~ l;y~t ls be~t ormed in ~itu usually by mixing the deo~gea~tecl i~t ~o~ven~ and --. .
~eat olefin, followed by ~he add~tion o~ the ~xce~s m~tal halide o Group IYB, and finally by the addition of the 10 ligand stabi~ized platinur~ complex ~o form the reac-tion mixtur~.
3) ~ter ~asing either Yaria~ion i or 2, the de-oxygenated catalyst containing reactlon ~lxture i~ pre~ur-lzed with C0 and hydrogen and heated until t}ie ldehyd~
pro~uct i8 ~ormad.
~ ) An e3pecially pre~rred modi~ca~:Zon, whieh ~irlimizes both 'che induction period and ~he isomerization of the ol fin, i8 the ollowing: the cata7y~t i~ formed in a deoa:ygena~ed solvent, t7he cal:aly~t qolution ls pre~sur-20 i~t with carbon monoxide and hydro~ser~ and heated to ~hedesired reactiorl temperature; olein i8 then added neat or dissolv~d i~ a ~uitabl~ sol~en~ reActiorl miacture i3 a~itated under C0 an~ ~12 at the da~ d reaction ~emperature un~cil . he aldehycle product i~ formed.
5) A ~cond preferred modif~cation, i~ the use of di~persionq of. ~aid ligand-~tabili~ed platinum(II) halide complexes in low~melting gua~ernary alkyl sal~:s of trl-chlorostannate (II) or trichlorogerma~ate (II~ as catalys~s for the conversio~ of alpha-oleins ~o the corresponding lin~ar alkyl aldehyde.
_6_ - . . . . -, : .
. .
, LtGAND-5T~ ZEI) PIATINUM E~ROFOE?MYLA~ION
C~TAIXSTS
S~me ligand-~abiliz~d.l, platinl~m(II) halide, Group IVB metal halide co~plexe~ are ~own in the litera~
ture and me~hod~ for ~be~r preparation haY~ been de~cribed*.
`-' One conver3ient mode of preparat-lon in ~itu i8 to mix a ~olu-~iorl of plai:inum(II) halide complex ~uch a~ PtCl2[PtC~Hs)3~
with ~ lar~3;e mola~ esc~eqs o~ ~roup IVB metaL halide, pr~er-e~ially SnCl2.
10The three cGmponent ligand-~tabillzed platinum(II) ca~caly~t compos~tion of thi~ ventio~ cor~ t~ e~ntlally 1~ platirlum (II ) halides
2. ~roup VBy VIB, or VIIB donor ligand3, and . Group IVB metal IhalidQ~
1. The pla~ (II) haLid~ compoflent~; employed in th~ cat 1~ colapo~ition are preferably the dichlorlde or ~he dibromide5 in ~hat ordeE~ ~hese d~ hal~des, in order ~o be effective for the ~elective ~nd preferential hydrolormyla-on proce~s, mu~t include at least orle Group VB, VIB or VIIB
donor ligand and Group IVB metal ha~id~s, de~crib~d more ful:Ly below:
2. Each Group VB donor llgand contai~ one or more pho~phorus an~mony or ars~nic atoms, pr erably in ~he trivalent state, bonded to one or more hy~xo~rbyl radicals3 said ratical~ b~:ing selected from the group consisting of aryl, alkyl, and substituted aryl radicals containing less *For exam~le: R. D. Cra~er et al, 3. A. Che~. Soc., 85, 16gl (196~5).
~7~
1:han 20 carbon atom~ . I llu~trative ~mple~ of ~3ui~able Group VB donor ligarld~ are P(c~3Hs)~H3~2~ P(C~Is)~, A8 (Ca~)a, P (n~ He ) 9 ~ P (~ce~E5 ) 3 ~ P (p-C~3 C0a~ ) 9 and (C~H~ ) 2PCH2CH2P (CaH3 ) 2
1. The pla~ (II) haLid~ compoflent~; employed in th~ cat 1~ colapo~ition are preferably the dichlorlde or ~he dibromide5 in ~hat ordeE~ ~hese d~ hal~des, in order ~o be effective for the ~elective ~nd preferential hydrolormyla-on proce~s, mu~t include at least orle Group VB, VIB or VIIB
donor ligand and Group IVB metal ha~id~s, de~crib~d more ful:Ly below:
2. Each Group VB donor llgand contai~ one or more pho~phorus an~mony or ars~nic atoms, pr erably in ~he trivalent state, bonded to one or more hy~xo~rbyl radicals3 said ratical~ b~:ing selected from the group consisting of aryl, alkyl, and substituted aryl radicals containing less *For exam~le: R. D. Cra~er et al, 3. A. Che~. Soc., 85, 16gl (196~5).
~7~
1:han 20 carbon atom~ . I llu~trative ~mple~ of ~3ui~able Group VB donor ligarld~ are P(c~3Hs)~H3~2~ P(C~Is)~, A8 (Ca~)a, P (n~ He ) 9 ~ P (~ce~E5 ) 3 ~ P (p-C~3 C0a~ ) 9 and (C~H~ ) 2PCH2CH2P (CaH3 ) 2
3. Group I~ D~etal hal:ides which can be utilized with tbe first two components [plat~ 3m(II) halide3 and Group VB, VIB or VIIB donor ligand~l include tin(II3 chloride, tin (II~ bromide, ti~ (II) ~odlde, tin (IV) chloride, and ge~manium (II 3 chloride .
Illu~ rative of suitablla ~igand-~tabilized plat-inum(II3 halide-Group IVB wetal halide ~el~ctive h~rdro~
formylation cataly~s are:
PtCl2[A~ (CO~s~3J2-SnC
PtC:la[P(C~Hs)~3] 2-SnCl2, PtCl2[P(C2~s)2(C2~ SnCl2, PtCl2~As (n-C~Ig)3J 2-SnC:12, PtCl2 EPCl ~G~H5 ~ 2J 2-SnC:1 PtCl2[ ~C8Hs)2P(CH2)2P(C~3Hs)2]~5nCl~
PtCl2 [ (C~Is ) 2AsC~2CH2As (C~Hs ) 2] -Sncl2 - Pt~::12[P(n-C~Hs)332 SnCl2, PtC 1~ [ P (CH~ ) 2C~H~; ] 2-SnCl;~5 PtCl2~Ptp CEI30C~H~)3~2~SnCl2, PtCl2~P(OC~!~H5)3]2-SnCl2, Pi C 12 [ P ( ~^C~ 3 . C~ ) 3 ] 2~ 2, PtCl2 ~S (C~Hs ) 2~ 2 -SnC 12 PtCl2 ~'3b (C~H5 )3 3 2-SnCl2 P'cCl (o-phenanthroline ) -SnC:12 K2PtC 1.; SnC 12 as well as the corresponding tin (IX) bromide, tin (II ~ iodide, .
tin(IV) chloride, and germanium(II) halide complexes.
Tables I to IV show evidence of the ~uitabillt:y of the above cla~ of ligand-~tabi.liz~d pla'ci~um(II)tlrou~ IV m~tal halides complexe~ as selec~v~ alld prefe.ren~:lally hydro--formyl~tion cataly~ ts .
A ~referred c:La~ o ~uitable hydroi~ormyl tion cataly~t~ oT~si~ts of dispersions of c~rl:ain ligand-~tabilized platinum(II) halide in quat~rnary ammoni~, pho~phoniufflt and/or arsonium sal~ of txichloros~anr~a~e (II) or trichloroge~manat~ . I llu~ra~ive examples of ~ueh platinum ca~alys~ c~mposl~lun~ which have be~n found ~ctive ~or the sel~ctive hydrofo1:mylation of lirlear ~-olefins to linear aldehydic produc~s iiJslude:
~ (C2H5).~N] ~SnCl3~ - Pt~::12~P(C~Is)3 [ (n-C~ ] [SnCl3] ~ "
~ (~ e~5)4Ag] ~;aCl3]- 19 7Hl~)4N~ ~SnC 13 J_ ~ (e2~15~4~ ~GeCl3] - ll [ ~C2Hs)~ [snclsl - PtCl2{P(p~C~3~CeiH~)3~2 1 ~C2EIS ) ~ [snc ls ~ ~ PtC~2 ~ P (n~ 3 1 2 t (C2HS~,N] ~SnC3L3] - Ptcl2lp(c~l3)~c~l2 Psef~!rably ~a~d quaternars~ ~alt~ ~hould be low~mel~ing qua-~ernary alkyl ~alt~ of trichIoro~ltan~ate (II~, C: . ~TIO OF TI~t (II 3 ~LIDE TO L~ STABILIZED
PLATI~U~f (II 3 COMPI.EX
~hile. ~he molar ratio of tin(II) chloride to the l~gand-s ~abilized platinum (II ) halide complex 1~ not cri~:ical, ehe expesimental worlc per~ormed indicates ~hat at lea t 1 mole of ti~(II) chloride ~or each mol2 o~ ligand-stabilized pla~inum(II) chloride complex is required for reproducibility and go~d selectivity. Preferably a ra~io o fro~ about 2 to ~O 8 mol~s of ein(II~ ehloride for each mole of ligand-s~abilized s~ 9~
platlnum~II) complex has been e~tablished to giv~ the opt:ilDum amour~t of linear para~finic aldehyde at gr~atly increased rate~ of hydroormylation. Thi~ preerred-ratio ~ s ~a~ed upon the hydroformylation of l-heptene .
D. ûXIDEoSUPPORl~D, NICKEL-CONT~INI~G
Th~ ox~de-supported, r~ickel-contai~ing amlnation cataly~ts of thi~ inveTltion ar~ ob~sined by the copr~cipi-tation of variou~ nickel ~alt~, as thelr carbonates or bicarbonates, in the presence of other met~l ~alt~ se~ected from Group~ IB, II, IIIB, VIA, VIIA and VIII of ~he Perlodic Table*. Preparation o ~aid cataly ts 1~ efec~ed by the additio~ of aqueou~ ~olutions of ~odium car~onate, ~odiu~
blcarborla~e and/or the carbonates of smmonia3 to so lutit~s of soluble ~ickel salts alqo contain~ng the solub1e salts of metal~ ~elected from Groups IB, II~ IIIB~ VIA, t~IA
and VIII. The precipitated9 carbonat~containing, material is isolated by f~ ration, washed, dried and calclned. The ~ickel content of said precipltated carbonate may varsr ~rom 2C) 5% up to a~out 75~ by weight and sa~d precipitated catalyst may al80 corltairl ~rarying quantitie~ of ~nagnesiu~, calci~m, strontium, barium, zinc, alumim~m, hrsmium, manganese, copper, coball:, tu~g~tetl a~d iron.
Preferred catalyst com~osi~ion~ consist o~ oxide-supporfed rlic~el catalysts containing from 5 to 75,¢ by weight of nickel, an~ also containing varying quantities of magne~- -ium, barium, aluminum and chromiura. Examples 42 to 51 pro-Yide exemplification of thiq preferred class vf catalyst or effecting the reducti~e amination o typical linear alkyl aldehyde substantially to the d~sired 7 inear alkyl primary amines.
-10_ ~See: F. Cotton and G. Wilkinson, "Advanced Ino~ganic Chemîstry, " Interscience, l962.
. - . .. .
.... , , . . . - - . ~ . .
- , . . : .. .
E . ~EACI ION TEMPERATURES
___ The eemperature ranges which can be Pmployed for the hydroormylation and reduc~iv~ a~lnation 3tep~ are variable~ which are depend~nt upon ex~er~mental factor~
including the olefin exmploy~d, tbe total pres~ure, th¢
mole ratio o hydrogen and carbon monox:Lde used, the COtl-CQntra~ions of reac~ant~ and ca~a:Lyst, and par~cularly the choice of plat~num and n~ckel cataly~t~. Starti~g with a ~yp~cal linear ~oleirl o 2 to 30 carbo~ atoms 10 . aDd Ptcl2~ptco~ls)s]~-sncl2 a~ a repre~entative hydro-fo~:mylation catalyst, an operable temperature rang~ or the fir~t, hydroorm~1~tiorl, st~p is iErom abou'c 25' to 125C at supera~mospher~c pxessures o greater than 100 p~ig. Likewi~e, the operable temperat~re ra~ge for the reductive ~mination i~ fr~m about .5~o 200C.
P. REAC:TIO S
T&e pre~sure ra~ge ~h~ch can b~ employed for the hydroformylation step T3 a Yariable wh:ich i~ also dependent on the factor~ ~entionad above. Using PtCl2~P(C0~s~2-SnGl2 as a representative catalyst~ and l-hept~ne as ~he linear alpha ol~fin component, an operable pressur~ range ig rom 100 to ~3000 psi~, with a ~ol~ ratio of H2:CO b~ing lol~
~hen a temperature range of rom about 25~ to 125C iLs ~mp loyed .
Likewise the total pres~ure of hydroge~ plus ammonia applied during the reductive a~nination step may ran8e from lOV to ~iOOO ps~ g, or greater, using the oxide-~upported nickel-containing catalysts of this in~ention.
. ' ' ~. .
. . .: ~ . . . ' , SOIV~
Both the hydrofox~uylatiorl and reduc ~lve aminatlo~
qteps may be run comreniently in the presence o~ an iLnert diluent. For the hytroonnyla~iorl s~ep experlmental dat~
dica~e ~he prefe~ed solvent~ are pol~r ke~one~ ~uch a~
- ace~one, methyl ethyl keton~, die~hyl ketone7 methyl propyl kato~e9 TDethyl i~obutyl kel:one, and acetophenone. ~lowever, other solvent3 i~ert to hydroformylation c~n be u~ed. The~e include ar~ma~ics ~uch as benzene~ toluene, ~lene~ and ~he like . Genera lly the re~ction i~ ~n ln the pre~ence of sufic~e~t lner~ solvent to di~perse the compone~ts of ~h~
reaction mixture; exce~ ert ~olvent does not appear to be ha~mfu 1.
Th~ preferred cla~s of ~ol~rent~ for the reduc~cive amiaation tep are alkanolsJ including m~thanol, ~thanol, i30pr~panol and ter~. butanoi.
n~
A~ previously indicated i~ ~h~ a~logous dl~cu~sion abQve, e~perimental variable~ are import n~ in arriving at reaction times. Generally, ~ubstantlal conver~ioos (~bou~
80 to 95%~ of the alpha-ol~in to the linear paraf~ ic aldehydes can a~most alway~ be accompli~h~d 6~ithin 2û hours with ~ to 6 hours representing the more us~aal reaction ti~e interval .
LikE~Wi91~! the reac tion times for the reduc ti~te amination step may exceed 20 hours, witb 4 to 6 hours again representi~g the more u5ual reaction time interval Experimentaï work indicates tha~c an initial molar ratio of up 'co about 500 to 1000 moles of alpha-alefin per -12_ mole of platln~n metal catalyst may be emp:loy~d ~n ~h~
fir~tJ hydrofo~mylation, ~tep. Thl~ min~mal ratio of about 0.001 mole~ o cataly~t p~r mole o totaî olefin i~
hereitl referred ~o as a '1catalytio rat Lo" or "catalg~ic amount." ~quch lowe~ ratios tl.e. 25 mole~ of ol~fitl sub-~tra~e per mole of platinum cat~ly~t eomplex~ are not haDful but are economically unattrac tiv~ . For thi~ r~a-~o~ ~he favored mole ra~io raTIge i~ from 100 to 500 mole~
of t~aL olefin per mole o platlnum cataly~t c~mpl~.
J. OIEFXNS AS SUBSTRA~iS
.
Olef~ ran~ing in ~arbon co~en~ ~r~m 2 up ~o 3n carbon a~oms can be ~mployed a~ ~ubs~rate~ for ~h~ oxo-amination r~action~. Illustrative of ~uleabl~ ~enmlnat (alpha) olefin ~ubstxate~ lnclude l-propene, l;bu ene~
l-penkPne, l-hexene, l-hepten~ octeDe, l-nonene, l~dec@n~
l-undecene, l-dodecane, l-tetradecene a~ well a~ their bigher h~mologues such as l-heptadecene~ l-octadecene, l-eicosene, l~tx~cosene, l-p~ntaco~ene. Illu~tratlve branched chain ~olefin ub~trate~ includ~ i~obut~lene, 2-methyl-1-pentene and 3-methyl-l~pen~en~. Illu~trat~v~
in~ernal and cyclic olei~s include 2-butene, 2 pentene, 2-heptene, and cyclohexene, etc. The~e ol~in sub~trata3 ~ay be utilized ia conjunct~on with one or more inert back-gsound solvents such as those men~ioned above. The olefi~s can be in t~e o~ of single, discrete compounds ar in the form of ~ixtures of ole~ins with or withou~ large qua~ti-~i~s of ~aturated hydrocarbo~. In the latter case these c~mpri~e mixtures of from 2 to 30 carbon at~ms. Table Vl ~how~ data or t~e hydroformylation of various olefins.
.. . ., ~.
..
K. RATIO OF HYDROGEN TO CARBON M~NOXIl:E
The H~/CQ ratio e~aployed during the hydro~
fonnylation step may vary ov~r the ran~e from 3û/1 o 1/~(~
when suitabl~ temperatures and to~al preqsure~ are em ployed~ A pre:erred narrower range i~ from 2/1 ~o 1/2 o hydrogen- to car~on ~o~oxid O
L IDENTIFICATION PRO~ DURES axe by one vr ~ore of th following analy lcal proc~dures - ga~ chromatography (gc), in:Erared7 elemesltal anal~sis and nuclear ma~netlc re~onance. IJnle8s otherwise spec:ified all percentages are by mole rather than weight or volllme, and ~11 temperatures are in cerltigrade rather than fahrenhei t .
M. CONVERSI017 as def:lned herein repre~erl~ the extent of eonver~ion of the reacting olefin ~o other pro-duc~s. Conver~ion 1~ e~pressed as a percerltile and i~ .
calculated by dividing the amoun of olefin or intermedla~e aldehydn con~u~ed during the hydroformyl~tion or reductiv~
amination steps, respectively, by the amour~ originally charged, and mul~iplying the quo~ent by }OO~
N. YIEI.D as deined her~ln, represen~s th~ effi ciency in catalyzing the des~red hydroformyla~i on or reduc-tive aminatiofl reaction relative to other und~sire~ reaction3.
In this instance linear alkyl primary amine form ~iorl is ehe desired conv~rslon. Yield is expressed as a percentile, and is calculated by dete~:mining the amount OI' l~e~r alkyl primary amine or linear aldehydic irltermediatQ formed, divided b9 the amount o ald~hyde or oLefin charged a~d multiplying the quoti~nt obtained by 100.
O. SELECTIVITY as defined herein is the effi- .
ciency in catalyzing a desired hydroformylation or reductive - 14.
-.
~nination reaction relatlve ~o other undeal~d re~ctlotl~.When a~olein~ ar~ to be hydrooxmylated7 hyd~oformulatio~
to the llnear parafini~ aldehydQ 1~ the desir~d con~er~
~ion. Selecti~tity i~ expre~d a~ a percen~ile, and 18 calculated by det~rmiDing the amount of llnear aldehyde produc~c fo~med, divided by ~he ~otal amount o aldehyde pr~duct~ o~med a~d multipl~ing t:he quotient obt~ined by 1~.
~ avlng de~cibed the i~e~tive prO~ 38 in general .
term~, the followlng ~æampl~s are! sul~mitted to ~upply speci~
ic and illustrative em~odimeslts.
EXIQIPIJ:~ 1 HYDROFO~MYLATION OF l-EIEPT~NE CATALYZED
BY ~IS (TRIPHE~YI.P~IOSPHINE ) P~TINUM (II ) CHIORIDE - STA~OUS CHI~RID}: CATALYST
~O~qP~X
To a ~i~50 ~1 gla33 lln~r of a rocking ~ltociave is ~dded 58 ~1 o methyl i~obutyl ketone and 7.9 ml (0.058 fnole) of l~hepte~e. The solutloF~ i~ deoxyge~ated s~ith nitrogen and û.325 g tl.~5 x lCI-3 mol~ ) o:~ SnC:12~ 2~120 i~
addéd to the mixture and ~tirred 2Q3 mlnutes uni:il d~s~olved.
Then PtGl2(PPh3)2y 0.229 g (2.9 ~ 10-~ mole), i~ added, ~nd ~he ~ixture ~tlrred or ~ urth ~ -g minute~ under a t~itro^
g~n purge. The catalyst solutio~ turn~ to a light yellow-greeni3h color, and although ~ome of the P~Cl2 (PPh~ ) 2 i~itially remalns undissolved, the mixture beeoT~es co~pletely homogeneou~ after a ~hort period of warming and ~irring u~der carbon monoxide and hydrogen. The loaded liner is then added 'co the autoc la~7e and the apparatus is de~xygena~d with nitrogen. Carbon monoxide, 750 psigJ and hydro~en, 7~iO psig, are then charged to the reactor and the reac~or is h~ated to 66C with rockiIlg for 3 hours, and ~he heat tl~rn~d of .
- 15_ . .. ..
.
Ater th~ app~ratus ~s cooled ~ld vented, 62 ml o a greeni~h-red solutior~ containing a small ~ount of dar~c sollds is recoYered. Ga~ chromatographic analysl~
re~Teals ~he ollow~ng re~ul~s: .
Co~er~io~ ole %3 100 Yield C~ aldehyde~ (mole ,~) 85 ~vle ra.io l~octylaldehyd~/2-methyl beptaldehyde 9/1 nerization ~ 2- and ~i~heptarle (mol~ ) 2.7 Th~ mi~slng 8.7 mol~ percent o l-hepten~ is 10 assum~d to ~a~e formed high boillng products whlch do no~
come of t}~e ga~ ~hromatograph under the corldition~ ~t which i~ wa~ op@rated.
E2Ak~ l.A
-- .
O~)A~NATION OF l~:PTENE TO n-OCTYL9~INE
CAI~ALYZED BY A. PI~TINUM(II)-STANNOUS C~ILORIDE
~:A~ALYST P~US AN OXIDE SUPPORTE~ N~CKEL CATALYST
To a 350 ml glas~ liner of a rocki~g autoclaYe is add~d 58 Dll o~ tvluen@ and 709 ~l (0.û58 mole) o l-hep~:e~e. .T~e ~olutio~ i8 deoxygenated with nitrogen and 0.~i25 g tl.4~ x 10~3 mole) of SnCl2~2H20 i~ added to the mixture a~d sti~ed 2~3 minutes until di~solved. Then PtCl2~PPh3)2, 0.229 g (2.9 x 10~4 mole)3 ls added, and ~che ~lxture ~tirred ~or further 2~ minute~ under ~ nitrogen purg~. The c~talyst ~olueion ~urn ~o a ligh~ y~llow-greeni~h color, and although some of the PtCl2(PPh3)2 initially remains undi~solved, the mixture becomes ~o~pletely ho~ogerleous after a short period of warming and stirring under carl~on monoxide and hydrogeD. The loaded liner i~
then added to the au~oclave and the apparatus i~ deoxygenated with nitrogen. Car~on monoxide, 750 psig, and hydrogen, 750 ~16-1 L~44~1 p~ig, are then charged to the reac tor and th~ reac~or i~ he~ted to 6~iC with roc~sing ~or ~ hour~9 and ~h~ heat turned off. Ç:.C. conf~ms Ca aldehyd~ yil31d of abou~
O . 049 mo le .
To the above glas~ liner ~on~inirlg û.C~9 mole octylalde~ayde are added t~ g o~ ~he oxid~upported ~iLckel GatalySt p~epa~ed according to Ph~ procedur@ of ~xample ~2 aad ~0 ml o~ ~ethanol. Th~ reac lon v~ 1 ls d~oacygenated, 10 g oi!~ a~moaia injected ~Tl from th~ side ampoule, and 10 ~he whole pre3~ured to 12ûC) psig with hydrogerln T~ r~ac~
eiO~ ml~ture is th~ heated to 1~0C with agi~ca~ion~ and held at temperature ~or our bour~.
Ater cooling and verlting, the li~uid product i8 ~parated ~om the solid cataly~t by iltratiorl and ~ulb~ected ~co analys~ ~y t:~Co A four g yield of o~tylam~n~ ls i~o~
lated by ~ractional distillatiorl g~7ing a ~lectivity of 88 moie % t~ n~oe1:ylamine and a ~ld of 0.031 ~nole <:f octylamine~ .
.,' ~ . .
21)- ~IYD~OFORMYIATIO~ OF l-~PTENE CA~LY2ED BY PIATI~UM
BI~IETALLIC COMPLEXES ~ E~TECT OF
GROIJP IBV ME'rAL E~LIDE CO~SITION
Table I wh~ch follow, shoti73 the da~a obtained whe~ the de~i~ated caitalyst a~ employed in the hydro-for~ylatioR of l-h~pt~ne ~ g the procedure of Example 1.
All the ex~mples ~hown in Table I wera carried ou~ under the following conlditions:
Solvent - methyl isobutyl k~tone l EIeptene, o.88 mole per liter l-Heptene/PtC12(PPh3)2 molar ratio, 200/1 lnJ PtC 12 (PPh3 ) 2 mo lar ra tio ~ 5/
~2/CO a~ lJ 1, 1500 p~ig Reaction kQmperatu~e ~ 66C
~17-A~ the data of Table L lndlc~te, meaning:ul hyd~o~
ormylation o l~hept~n~ to octyl aldehyde i3 obtained under ol~r prQ~erred mild reaetiorl condition~ wh0~ ~ ligand-~tabill~ed platinum halide comple2~ and the Group IVl~ ~etal halide exemplif:led by ~tannou~ chloride, s~annic chlorlde, and g~rmanium(II~ chlorid~, ~r~ u~ied toge~:her to form a catalyst. I~ the absence of these Group IYB metal halides - 3uch liga~d-~tabilized plat~num halide comple~es are not efiEect~e hydroormylation cataly~ts under our preferred mild reacsion conditions.
E~AMPI;E:S 6- 11 ~_.
~IYDROFO~YI~TII:~l!il OF loEIEPTENE C~TAL~ZED :~
PLATII!I~ BIMETAI.LIC COMPIEXES - I~F~ECT OF
HAIl:)GE~, PSEUDO~ )GEN AN3~ STANNOUS HALIDE Ct:)~OSIllON
Table II ~hich 0110w3, shvws the data ob~cai~ed when the de~igRated caPaly3t~ are employed ill the hydro~
formylat~o~ of l-h~p~en~ us~ng t-he procedure of Example 1.
All the example3 ~hown ~n Table II were carried ou~ under the condition3 e~cribed ln Ex~mple 1 and Table I.
As the data o~ Table II ~ndicat~, ~eanltlg ul }~ydro:~ormyla~ion of l~heptene ~o octyl ald2hyde i~ ob~
tained under our pre~rred mild reaction condi~ions when ligand ~tat:iilized platlnum b~lide complex~s and stanrlous halids metal s~lts are u~ed together ~o form a cataly~.
The effec~ s o the halide~ n the direction Cl ~ Br > I. The p~eudo-halide ryanide ligand wa~ not ~ffective in prom~ting hydroformylation by the catalyst Pt(CN)2(PPh~)2 under our pr~ferred mild r~action conditions.
IPI.ES ~2- 18 __ EI~DROFOR~YLATION OF l-HEPTE~E CATALYZED BY
PLATINUM BI~ETALLIC COMPLEXES - EFFECT OF
~IGANDS WITH GROUPS YB, VIB, VI:I:B DONOR ATOMS
Table III which follaws7 shows the da~a obtairled when the des~ gnated catalyst~ are e~nployed irl ~he hydro-formylation of l-heptene uslng the pro edure of Example 1.
o~
I ~ I
h .
~: ~
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~ ~ O ~L
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Q~
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. :1 s~
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a:
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~ ~U
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o ~u ~ o e ~ c s:L.
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.
.
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.. : - -. : . ~ .. . . .
f.~
o~
c ~ cr~
~ ~o cr~
o c t.1 0 P- . I1 3 ~ ; cu c~
(~.) 1~ e:
~ Q.3 ~ e . ~ aJ
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~ ,~; ~ ~ O
~ O ~
.. ~ 15-l C~ . . . . .
~G
U
~a ' ~3 ~ . ' .
E~ ~ ~o O ~
~11 - .
æ~ 8 8 -~U 8 `
~C C~
~: U~ N + U~ ~J
+ + ~n ~ OJ + _~
~ N N ~~ ~
_ ~ ~ e o~ ~;
' P.
14 11.~ ~ 1~ N ~ ~ ~
P~ ~ ¢ O
~J N ~ t:
N ~ I N
X ~ ~ H`--C.~1-1 Ll ~1 , J~ 1") a~
~ P~ ~
a ~ ~ C~ O -X _l ~1 a~
. ., . , ~
1~4 ~
.~
V~ ~ C~ O
V) ~0 r~
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a.) "
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t~) O 1~ N
O t~
o~o ~--1 N
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~ I
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,_, ~d r-l ~, Ln~D O _~ ~ N O
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a> v, o~ a o ~ h o. o o cr~ o cr~ a~
::,C o ~ .
N N ~
X G ,~ O
r-~ N N ¢ r--l O ~1 7--I
H r-l N ~ $1 H ~L) ~ N N ~ N ~ +~ N ~ 4 "_1 t~) ~ ¢ S ,5: N
~d t~
1~. _, ¢~,U:) O ~ yN O~
N ~ N N N N
D~ ~ ~4 C4 ~ N ~) ~Il~ ~ ~ 00 ~
~ ~ ~d - .
:
Illu~ rative of suitablla ~igand-~tabilized plat-inum(II3 halide-Group IVB wetal halide ~el~ctive h~rdro~
formylation cataly~s are:
PtCl2[A~ (CO~s~3J2-SnC
PtC:la[P(C~Hs)~3] 2-SnCl2, PtCl2[P(C2~s)2(C2~ SnCl2, PtCl2~As (n-C~Ig)3J 2-SnC:12, PtCl2 EPCl ~G~H5 ~ 2J 2-SnC:1 PtCl2[ ~C8Hs)2P(CH2)2P(C~3Hs)2]~5nCl~
PtCl2 [ (C~Is ) 2AsC~2CH2As (C~Hs ) 2] -Sncl2 - Pt~::12[P(n-C~Hs)332 SnCl2, PtC 1~ [ P (CH~ ) 2C~H~; ] 2-SnCl;~5 PtCl2~Ptp CEI30C~H~)3~2~SnCl2, PtCl2~P(OC~!~H5)3]2-SnCl2, Pi C 12 [ P ( ~^C~ 3 . C~ ) 3 ] 2~ 2, PtCl2 ~S (C~Hs ) 2~ 2 -SnC 12 PtCl2 ~'3b (C~H5 )3 3 2-SnCl2 P'cCl (o-phenanthroline ) -SnC:12 K2PtC 1.; SnC 12 as well as the corresponding tin (IX) bromide, tin (II ~ iodide, .
tin(IV) chloride, and germanium(II) halide complexes.
Tables I to IV show evidence of the ~uitabillt:y of the above cla~ of ligand-~tabi.liz~d pla'ci~um(II)tlrou~ IV m~tal halides complexe~ as selec~v~ alld prefe.ren~:lally hydro--formyl~tion cataly~ ts .
A ~referred c:La~ o ~uitable hydroi~ormyl tion cataly~t~ oT~si~ts of dispersions of c~rl:ain ligand-~tabilized platinum(II) halide in quat~rnary ammoni~, pho~phoniufflt and/or arsonium sal~ of txichloros~anr~a~e (II) or trichloroge~manat~ . I llu~ra~ive examples of ~ueh platinum ca~alys~ c~mposl~lun~ which have be~n found ~ctive ~or the sel~ctive hydrofo1:mylation of lirlear ~-olefins to linear aldehydic produc~s iiJslude:
~ (C2H5).~N] ~SnCl3~ - Pt~::12~P(C~Is)3 [ (n-C~ ] [SnCl3] ~ "
~ (~ e~5)4Ag] ~;aCl3]- 19 7Hl~)4N~ ~SnC 13 J_ ~ (e2~15~4~ ~GeCl3] - ll [ ~C2Hs)~ [snclsl - PtCl2{P(p~C~3~CeiH~)3~2 1 ~C2EIS ) ~ [snc ls ~ ~ PtC~2 ~ P (n~ 3 1 2 t (C2HS~,N] ~SnC3L3] - Ptcl2lp(c~l3)~c~l2 Psef~!rably ~a~d quaternars~ ~alt~ ~hould be low~mel~ing qua-~ernary alkyl ~alt~ of trichIoro~ltan~ate (II~, C: . ~TIO OF TI~t (II 3 ~LIDE TO L~ STABILIZED
PLATI~U~f (II 3 COMPI.EX
~hile. ~he molar ratio of tin(II) chloride to the l~gand-s ~abilized platinum (II ) halide complex 1~ not cri~:ical, ehe expesimental worlc per~ormed indicates ~hat at lea t 1 mole of ti~(II) chloride ~or each mol2 o~ ligand-stabilized pla~inum(II) chloride complex is required for reproducibility and go~d selectivity. Preferably a ra~io o fro~ about 2 to ~O 8 mol~s of ein(II~ ehloride for each mole of ligand-s~abilized s~ 9~
platlnum~II) complex has been e~tablished to giv~ the opt:ilDum amour~t of linear para~finic aldehyde at gr~atly increased rate~ of hydroormylation. Thi~ preerred-ratio ~ s ~a~ed upon the hydroformylation of l-heptene .
D. ûXIDEoSUPPORl~D, NICKEL-CONT~INI~G
Th~ ox~de-supported, r~ickel-contai~ing amlnation cataly~ts of thi~ inveTltion ar~ ob~sined by the copr~cipi-tation of variou~ nickel ~alt~, as thelr carbonates or bicarbonates, in the presence of other met~l ~alt~ se~ected from Group~ IB, II, IIIB, VIA, VIIA and VIII of ~he Perlodic Table*. Preparation o ~aid cataly ts 1~ efec~ed by the additio~ of aqueou~ ~olutions of ~odium car~onate, ~odiu~
blcarborla~e and/or the carbonates of smmonia3 to so lutit~s of soluble ~ickel salts alqo contain~ng the solub1e salts of metal~ ~elected from Groups IB, II~ IIIB~ VIA, t~IA
and VIII. The precipitated9 carbonat~containing, material is isolated by f~ ration, washed, dried and calclned. The ~ickel content of said precipltated carbonate may varsr ~rom 2C) 5% up to a~out 75~ by weight and sa~d precipitated catalyst may al80 corltairl ~rarying quantitie~ of ~nagnesiu~, calci~m, strontium, barium, zinc, alumim~m, hrsmium, manganese, copper, coball:, tu~g~tetl a~d iron.
Preferred catalyst com~osi~ion~ consist o~ oxide-supporfed rlic~el catalysts containing from 5 to 75,¢ by weight of nickel, an~ also containing varying quantities of magne~- -ium, barium, aluminum and chromiura. Examples 42 to 51 pro-Yide exemplification of thiq preferred class vf catalyst or effecting the reducti~e amination o typical linear alkyl aldehyde substantially to the d~sired 7 inear alkyl primary amines.
-10_ ~See: F. Cotton and G. Wilkinson, "Advanced Ino~ganic Chemîstry, " Interscience, l962.
. - . .. .
.... , , . . . - - . ~ . .
- , . . : .. .
E . ~EACI ION TEMPERATURES
___ The eemperature ranges which can be Pmployed for the hydroormylation and reduc~iv~ a~lnation 3tep~ are variable~ which are depend~nt upon ex~er~mental factor~
including the olefin exmploy~d, tbe total pres~ure, th¢
mole ratio o hydrogen and carbon monox:Lde used, the COtl-CQntra~ions of reac~ant~ and ca~a:Lyst, and par~cularly the choice of plat~num and n~ckel cataly~t~. Starti~g with a ~yp~cal linear ~oleirl o 2 to 30 carbo~ atoms 10 . aDd Ptcl2~ptco~ls)s]~-sncl2 a~ a repre~entative hydro-fo~:mylation catalyst, an operable temperature rang~ or the fir~t, hydroorm~1~tiorl, st~p is iErom abou'c 25' to 125C at supera~mospher~c pxessures o greater than 100 p~ig. Likewi~e, the operable temperat~re ra~ge for the reductive ~mination i~ fr~m about .5~o 200C.
P. REAC:TIO S
T&e pre~sure ra~ge ~h~ch can b~ employed for the hydroformylation step T3 a Yariable wh:ich i~ also dependent on the factor~ ~entionad above. Using PtCl2~P(C0~s~2-SnGl2 as a representative catalyst~ and l-hept~ne as ~he linear alpha ol~fin component, an operable pressur~ range ig rom 100 to ~3000 psi~, with a ~ol~ ratio of H2:CO b~ing lol~
~hen a temperature range of rom about 25~ to 125C iLs ~mp loyed .
Likewise the total pres~ure of hydroge~ plus ammonia applied during the reductive a~nination step may ran8e from lOV to ~iOOO ps~ g, or greater, using the oxide-~upported nickel-containing catalysts of this in~ention.
. ' ' ~. .
. . .: ~ . . . ' , SOIV~
Both the hydrofox~uylatiorl and reduc ~lve aminatlo~
qteps may be run comreniently in the presence o~ an iLnert diluent. For the hytroonnyla~iorl s~ep experlmental dat~
dica~e ~he prefe~ed solvent~ are pol~r ke~one~ ~uch a~
- ace~one, methyl ethyl keton~, die~hyl ketone7 methyl propyl kato~e9 TDethyl i~obutyl kel:one, and acetophenone. ~lowever, other solvent3 i~ert to hydroformylation c~n be u~ed. The~e include ar~ma~ics ~uch as benzene~ toluene, ~lene~ and ~he like . Genera lly the re~ction i~ ~n ln the pre~ence of sufic~e~t lner~ solvent to di~perse the compone~ts of ~h~
reaction mixture; exce~ ert ~olvent does not appear to be ha~mfu 1.
Th~ preferred cla~s of ~ol~rent~ for the reduc~cive amiaation tep are alkanolsJ including m~thanol, ~thanol, i30pr~panol and ter~. butanoi.
n~
A~ previously indicated i~ ~h~ a~logous dl~cu~sion abQve, e~perimental variable~ are import n~ in arriving at reaction times. Generally, ~ubstantlal conver~ioos (~bou~
80 to 95%~ of the alpha-ol~in to the linear paraf~ ic aldehydes can a~most alway~ be accompli~h~d 6~ithin 2û hours with ~ to 6 hours representing the more us~aal reaction ti~e interval .
LikE~Wi91~! the reac tion times for the reduc ti~te amination step may exceed 20 hours, witb 4 to 6 hours again representi~g the more u5ual reaction time interval Experimentaï work indicates tha~c an initial molar ratio of up 'co about 500 to 1000 moles of alpha-alefin per -12_ mole of platln~n metal catalyst may be emp:loy~d ~n ~h~
fir~tJ hydrofo~mylation, ~tep. Thl~ min~mal ratio of about 0.001 mole~ o cataly~t p~r mole o totaî olefin i~
hereitl referred ~o as a '1catalytio rat Lo" or "catalg~ic amount." ~quch lowe~ ratios tl.e. 25 mole~ of ol~fitl sub-~tra~e per mole of platinum cat~ly~t eomplex~ are not haDful but are economically unattrac tiv~ . For thi~ r~a-~o~ ~he favored mole ra~io raTIge i~ from 100 to 500 mole~
of t~aL olefin per mole o platlnum cataly~t c~mpl~.
J. OIEFXNS AS SUBSTRA~iS
.
Olef~ ran~ing in ~arbon co~en~ ~r~m 2 up ~o 3n carbon a~oms can be ~mployed a~ ~ubs~rate~ for ~h~ oxo-amination r~action~. Illustrative of ~uleabl~ ~enmlnat (alpha) olefin ~ubstxate~ lnclude l-propene, l;bu ene~
l-penkPne, l-hexene, l-hepten~ octeDe, l-nonene, l~dec@n~
l-undecene, l-dodecane, l-tetradecene a~ well a~ their bigher h~mologues such as l-heptadecene~ l-octadecene, l-eicosene, l~tx~cosene, l-p~ntaco~ene. Illu~tratlve branched chain ~olefin ub~trate~ includ~ i~obut~lene, 2-methyl-1-pentene and 3-methyl-l~pen~en~. Illu~trat~v~
in~ernal and cyclic olei~s include 2-butene, 2 pentene, 2-heptene, and cyclohexene, etc. The~e ol~in sub~trata3 ~ay be utilized ia conjunct~on with one or more inert back-gsound solvents such as those men~ioned above. The olefi~s can be in t~e o~ of single, discrete compounds ar in the form of ~ixtures of ole~ins with or withou~ large qua~ti-~i~s of ~aturated hydrocarbo~. In the latter case these c~mpri~e mixtures of from 2 to 30 carbon at~ms. Table Vl ~how~ data or t~e hydroformylation of various olefins.
.. . ., ~.
..
K. RATIO OF HYDROGEN TO CARBON M~NOXIl:E
The H~/CQ ratio e~aployed during the hydro~
fonnylation step may vary ov~r the ran~e from 3û/1 o 1/~(~
when suitabl~ temperatures and to~al preqsure~ are em ployed~ A pre:erred narrower range i~ from 2/1 ~o 1/2 o hydrogen- to car~on ~o~oxid O
L IDENTIFICATION PRO~ DURES axe by one vr ~ore of th following analy lcal proc~dures - ga~ chromatography (gc), in:Erared7 elemesltal anal~sis and nuclear ma~netlc re~onance. IJnle8s otherwise spec:ified all percentages are by mole rather than weight or volllme, and ~11 temperatures are in cerltigrade rather than fahrenhei t .
M. CONVERSI017 as def:lned herein repre~erl~ the extent of eonver~ion of the reacting olefin ~o other pro-duc~s. Conver~ion 1~ e~pressed as a percerltile and i~ .
calculated by dividing the amoun of olefin or intermedla~e aldehydn con~u~ed during the hydroformyl~tion or reductiv~
amination steps, respectively, by the amour~ originally charged, and mul~iplying the quo~ent by }OO~
N. YIEI.D as deined her~ln, represen~s th~ effi ciency in catalyzing the des~red hydroformyla~i on or reduc-tive aminatiofl reaction relative to other und~sire~ reaction3.
In this instance linear alkyl primary amine form ~iorl is ehe desired conv~rslon. Yield is expressed as a percentile, and is calculated by dete~:mining the amount OI' l~e~r alkyl primary amine or linear aldehydic irltermediatQ formed, divided b9 the amount o ald~hyde or oLefin charged a~d multiplying the quoti~nt obtained by 100.
O. SELECTIVITY as defined herein is the effi- .
ciency in catalyzing a desired hydroformylation or reductive - 14.
-.
~nination reaction relatlve ~o other undeal~d re~ctlotl~.When a~olein~ ar~ to be hydrooxmylated7 hyd~oformulatio~
to the llnear parafini~ aldehydQ 1~ the desir~d con~er~
~ion. Selecti~tity i~ expre~d a~ a percen~ile, and 18 calculated by det~rmiDing the amount of llnear aldehyde produc~c fo~med, divided by ~he ~otal amount o aldehyde pr~duct~ o~med a~d multipl~ing t:he quotient obt~ined by 1~.
~ avlng de~cibed the i~e~tive prO~ 38 in general .
term~, the followlng ~æampl~s are! sul~mitted to ~upply speci~
ic and illustrative em~odimeslts.
EXIQIPIJ:~ 1 HYDROFO~MYLATION OF l-EIEPT~NE CATALYZED
BY ~IS (TRIPHE~YI.P~IOSPHINE ) P~TINUM (II ) CHIORIDE - STA~OUS CHI~RID}: CATALYST
~O~qP~X
To a ~i~50 ~1 gla33 lln~r of a rocking ~ltociave is ~dded 58 ~1 o methyl i~obutyl ketone and 7.9 ml (0.058 fnole) of l~hepte~e. The solutloF~ i~ deoxyge~ated s~ith nitrogen and û.325 g tl.~5 x lCI-3 mol~ ) o:~ SnC:12~ 2~120 i~
addéd to the mixture and ~tirred 2Q3 mlnutes uni:il d~s~olved.
Then PtGl2(PPh3)2y 0.229 g (2.9 ~ 10-~ mole), i~ added, ~nd ~he ~ixture ~tlrred or ~ urth ~ -g minute~ under a t~itro^
g~n purge. The catalyst solutio~ turn~ to a light yellow-greeni3h color, and although ~ome of the P~Cl2 (PPh~ ) 2 i~itially remalns undissolved, the mixture beeoT~es co~pletely homogeneou~ after a ~hort period of warming and ~irring u~der carbon monoxide and hydrogen. The loaded liner is then added 'co the autoc la~7e and the apparatus is de~xygena~d with nitrogen. Carbon monoxide, 750 psigJ and hydro~en, 7~iO psig, are then charged to the reactor and the reac~or is h~ated to 66C with rockiIlg for 3 hours, and ~he heat tl~rn~d of .
- 15_ . .. ..
.
Ater th~ app~ratus ~s cooled ~ld vented, 62 ml o a greeni~h-red solutior~ containing a small ~ount of dar~c sollds is recoYered. Ga~ chromatographic analysl~
re~Teals ~he ollow~ng re~ul~s: .
Co~er~io~ ole %3 100 Yield C~ aldehyde~ (mole ,~) 85 ~vle ra.io l~octylaldehyd~/2-methyl beptaldehyde 9/1 nerization ~ 2- and ~i~heptarle (mol~ ) 2.7 Th~ mi~slng 8.7 mol~ percent o l-hepten~ is 10 assum~d to ~a~e formed high boillng products whlch do no~
come of t}~e ga~ ~hromatograph under the corldition~ ~t which i~ wa~ op@rated.
E2Ak~ l.A
-- .
O~)A~NATION OF l~:PTENE TO n-OCTYL9~INE
CAI~ALYZED BY A. PI~TINUM(II)-STANNOUS C~ILORIDE
~:A~ALYST P~US AN OXIDE SUPPORTE~ N~CKEL CATALYST
To a 350 ml glas~ liner of a rocki~g autoclaYe is add~d 58 Dll o~ tvluen@ and 709 ~l (0.û58 mole) o l-hep~:e~e. .T~e ~olutio~ i8 deoxygenated with nitrogen and 0.~i25 g tl.4~ x 10~3 mole) of SnCl2~2H20 i~ added to the mixture a~d sti~ed 2~3 minutes until di~solved. Then PtCl2~PPh3)2, 0.229 g (2.9 x 10~4 mole)3 ls added, and ~che ~lxture ~tirred ~or further 2~ minute~ under ~ nitrogen purg~. The c~talyst ~olueion ~urn ~o a ligh~ y~llow-greeni~h color, and although some of the PtCl2(PPh3)2 initially remains undi~solved, the mixture becomes ~o~pletely ho~ogerleous after a short period of warming and stirring under carl~on monoxide and hydrogeD. The loaded liner i~
then added to the au~oclave and the apparatus i~ deoxygenated with nitrogen. Car~on monoxide, 750 psig, and hydrogen, 750 ~16-1 L~44~1 p~ig, are then charged to the reac tor and th~ reac~or i~ he~ted to 6~iC with roc~sing ~or ~ hour~9 and ~h~ heat turned off. Ç:.C. conf~ms Ca aldehyd~ yil31d of abou~
O . 049 mo le .
To the above glas~ liner ~on~inirlg û.C~9 mole octylalde~ayde are added t~ g o~ ~he oxid~upported ~iLckel GatalySt p~epa~ed according to Ph~ procedur@ of ~xample ~2 aad ~0 ml o~ ~ethanol. Th~ reac lon v~ 1 ls d~oacygenated, 10 g oi!~ a~moaia injected ~Tl from th~ side ampoule, and 10 ~he whole pre3~ured to 12ûC) psig with hydrogerln T~ r~ac~
eiO~ ml~ture is th~ heated to 1~0C with agi~ca~ion~ and held at temperature ~or our bour~.
Ater cooling and verlting, the li~uid product i8 ~parated ~om the solid cataly~t by iltratiorl and ~ulb~ected ~co analys~ ~y t:~Co A four g yield of o~tylam~n~ ls i~o~
lated by ~ractional distillatiorl g~7ing a ~lectivity of 88 moie % t~ n~oe1:ylamine and a ~ld of 0.031 ~nole <:f octylamine~ .
.,' ~ . .
21)- ~IYD~OFORMYIATIO~ OF l-~PTENE CA~LY2ED BY PIATI~UM
BI~IETALLIC COMPLEXES ~ E~TECT OF
GROIJP IBV ME'rAL E~LIDE CO~SITION
Table I wh~ch follow, shoti73 the da~a obtained whe~ the de~i~ated caitalyst a~ employed in the hydro-for~ylatioR of l-h~pt~ne ~ g the procedure of Example 1.
All the ex~mples ~hown in Table I wera carried ou~ under the following conlditions:
Solvent - methyl isobutyl k~tone l EIeptene, o.88 mole per liter l-Heptene/PtC12(PPh3)2 molar ratio, 200/1 lnJ PtC 12 (PPh3 ) 2 mo lar ra tio ~ 5/
~2/CO a~ lJ 1, 1500 p~ig Reaction kQmperatu~e ~ 66C
~17-A~ the data of Table L lndlc~te, meaning:ul hyd~o~
ormylation o l~hept~n~ to octyl aldehyde i3 obtained under ol~r prQ~erred mild reaetiorl condition~ wh0~ ~ ligand-~tabill~ed platinum halide comple2~ and the Group IVl~ ~etal halide exemplif:led by ~tannou~ chloride, s~annic chlorlde, and g~rmanium(II~ chlorid~, ~r~ u~ied toge~:her to form a catalyst. I~ the absence of these Group IYB metal halides - 3uch liga~d-~tabilized plat~num halide comple~es are not efiEect~e hydroormylation cataly~ts under our preferred mild reacsion conditions.
E~AMPI;E:S 6- 11 ~_.
~IYDROFO~YI~TII:~l!il OF loEIEPTENE C~TAL~ZED :~
PLATII!I~ BIMETAI.LIC COMPIEXES - I~F~ECT OF
HAIl:)GE~, PSEUDO~ )GEN AN3~ STANNOUS HALIDE Ct:)~OSIllON
Table II ~hich 0110w3, shvws the data ob~cai~ed when the de~igRated caPaly3t~ are employed ill the hydro~
formylat~o~ of l-h~p~en~ us~ng t-he procedure of Example 1.
All the example3 ~hown ~n Table II were carried ou~ under the condition3 e~cribed ln Ex~mple 1 and Table I.
As the data o~ Table II ~ndicat~, ~eanltlg ul }~ydro:~ormyla~ion of l~heptene ~o octyl ald2hyde i~ ob~
tained under our pre~rred mild reaction condi~ions when ligand ~tat:iilized platlnum b~lide complex~s and stanrlous halids metal s~lts are u~ed together ~o form a cataly~.
The effec~ s o the halide~ n the direction Cl ~ Br > I. The p~eudo-halide ryanide ligand wa~ not ~ffective in prom~ting hydroformylation by the catalyst Pt(CN)2(PPh~)2 under our pr~ferred mild r~action conditions.
IPI.ES ~2- 18 __ EI~DROFOR~YLATION OF l-HEPTE~E CATALYZED BY
PLATINUM BI~ETALLIC COMPLEXES - EFFECT OF
~IGANDS WITH GROUPS YB, VIB, VI:I:B DONOR ATOMS
Table III which follaws7 shows the da~a obtairled when the des~ gnated catalyst~ are e~nployed irl ~he hydro-formylation of l-heptene uslng the pro edure of Example 1.
o~
I ~ I
h .
~: ~
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o c t.1 0 P- . I1 3 ~ ; cu c~
(~.) 1~ e:
~ Q.3 ~ e . ~ aJ
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~ O ~
.. ~ 15-l C~ . . . . .
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~a ' ~3 ~ . ' .
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~11 - .
æ~ 8 8 -~U 8 `
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~: U~ N + U~ ~J
+ + ~n ~ OJ + _~
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' P.
14 11.~ ~ 1~ N ~ ~ ~
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N ~ I N
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a ~ ~ C~ O -X _l ~1 a~
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t~) O 1~ N
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o~o ~--1 N
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a> v, o~ a o ~ h o. o o cr~ o cr~ a~
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X G ,~ O
r-~ N N ¢ r--l O ~1 7--I
H r-l N ~ $1 H ~L) ~ N N ~ N ~ +~ N ~ 4 "_1 t~) ~ ¢ S ,5: N
~d t~
1~. _, ¢~,U:) O ~ yN O~
N ~ N N N N
D~ ~ ~4 C4 ~ N ~) ~Il~ ~ ~ 00 ~
~ ~ ~d - .
:
4~LCD~
As the data of l'a~le II indicate, meaa~n~f hydrofo~nyla~ion of l-heptene to octyl aldeh7de i~ ob tained under our preferred ~n:ild reaction cond~tlon~ whe a srariety of llgands containlng Group VB, YIB and VIIB
donor ato~ns ~re u~ed to ~tabillze the platlnum halide c~mplexe~ tog~ther with the ~anr~ou~ halide m~al salt~
~o fo~m a cataly~. The pref~rred ligand3 appear to be eho~e conta~ning; a trlval~nt pho~phoru~ dorlo~ a~
E~PI ES 19~25 io }~YDROFORMYIATION ()F l-HEPl~NE CATALYZED
PLAllN(~M BIMETALIIC COMPLEXES - EFFECT
OF TRIVALENT PH :)SPHO~OUS IIGANDS
Table IV which follow~ shows the data obtain~d when the d~signa~ed cataly~ts are employ~d in ~he hydro-formylation o~ l-h~ptene using the procedure o Ex~pl~ 1.
All the examples ~hc~n in Table IV were carried out under the conditions descr bed in Example 1 a~d Table I.
A~ the data of Ta~le IV ind:lc~e, meaningfu~
hyd~oormylation of l-hepeens to octyl aldehyde $3 ob-tai~ed u~der our pre~erred mild reactioTI co~di~lon whe~
a Yasiety of tr~alerlt organo-pho~phoraus ligands are u~ed ~o modify Pt(II) chloride ~ ~tannou~ chloxid~ cata~
ly8t30 These includ~ ..riaryl9 triallyl~ ~ubstituted triar~rl and mixed alh:yl, aryl pho~phin~30 Triaryl pho3 phites, such a~ triphenyl phosphite, are a~o suitable.
Complexeq with mixed ~ubstituted pho~phines, such a~
PC1(Ph)2J are active, as are csmplexes with biden~ate phosphines ~uch as Ph2PC~I2CH2PPh2.
b~ ~
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~ ~ Lr~
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a) ~o o ~ o a~ o o ~ a~ _I ~ ~1 ~1 :r ~
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~d ~ ~rl ~1 ~I r~
~n ~ ~ o ~ ~ ~ ~ ~ .
X ~ ~I c~ ~ N .
r l N~, U~ +
o ~ * ~
t~ ~ ~ ~1 N t,~ t~l r_ p., 3 ~ C ~ ~ ~ :
~ 0 td C~
L~ 4 ~1 N ~ N t`J t~ t`l C~ ~ ~ r-l :
~ ~ ~ ~ ~ ~ ~ ~d .. .
~d :
o ~ c~ ~7 ¦ ~ ~ ~ ~ ~ N ~
:.
E~PLE 26 HYDROFORMYLATION OF PROPYLENE C~TALYZED BY
BIS (TRI~NYL~IOSPEIINE ) PLATINUM (II ) C:HI.ORIDE
DISPERSED IN TE:TRAETHYLA~ONIUM TRICHLORO~
An appropriate ly ~ized react~on ve~sel~ ~uch ~` a~ an autoclave, equipped with he~ting, oo1illg, agitatir~g;
pressur1zing mean~, and a ~ide ampou1e 8y~tem for intro-ducing char~;e~ u~der operating cond1tions, is chaxged w~th a ~ample of tetra~thy1=o~iLum tr.lch10ro~taTmate (II~ (14. 2 g ~0 mmole) and bi~ ttripheny1phosphine)p1at1num(II) chlo~
ride (:~S.16 g 4.0 mmole). The reactor sealed, purged with CO, a~d pres~ured to 1260 p~ig with 42 g o propylene (} mole) plu~ a 1:1 (Y/V) ~a~ mixtu~e o~ C/E12~ The mixture i~ heate~ to 80C, stirre~ for 5 hours at temperature~ and allowed to cool. Forty gram~ o~ y~llow liquid prGduct are recovered by decaDt~on ro~ he y llow cry~talline melt, and fract:T.onally di~tilled. Butgraldehyde~ (34.5 g 0.~ mole) are recovered from a fraction boiling 72-75C (l atm), and al~alyzed by ga~ chromatography usirlg a 10 t ~ 1/4'l colum~
of 20,~ OS-l 4 on chromasorb "G" heated ~o 1 0G with 100 cc/
min. P,le flow.
Yle ld o~ iso lated butyraldehyde~ 34 . 5 gram~
Yield of ~.~olal:~d butyraldehydes (ba3is propylene charged) 48 ~ole %
Purity of i~olated butyraldehydes 99~;
Se lec tivi ty to n -bu~yraldehyde 82~
- The rPcovered cry~talline melt cataly~t remains an active hydrofor~rlation catalyst aft~r butyraldehyde re-covery by decaneation. Additional ~butyrald2hyde may be p~eepared simply by recycIing the used dispersioll of platinum catalyst in quaternary alkyl trichlorostannate(II~ salt with -2~-fre~h propylene under the hydrofor~yla~ion condi~lon~ de~
~crlber ~E~ Yield data or the isol~ed butyr~ld~hyde3 prepared over a three cycL~ experiment using the ~m~ sample of bis(triphenylpho~phine~platin~m(lI) chlorlde disper~ed in etraethylam~onium trichloroqtannata~II) ar~ ~um~a~ized in Ta~l V.
~MPLES ~7-34 __ ~YDR~FO~MYLATIO~ OF PROPYL~ C~TALYZED BY
II~A~D-S~ABIIIZ~D PLATINUM(II) C~MP~EXES DISPERSED
I~ VARIOUS QUATERNARY 8ALTS OF ~RIC~ROS~A~N~TE(II) AND TRIC~IDROOERMANA~(II) __ In the~e examples the hydro~oxmylat~on of propyl~
ene to n-buty~aldehyde ~ carrled o~t in accordance ~ith the procedure of Example 26, but in the presence o~ vsriou~
liga~d s~abilizgd pl tinum(II) c~mplexe~ d~persed in a uumb~r of ~uaternary ~mmonium, pho3phonium and arsolllum ~alt~ of trlhalostannatetII) a~d trihaloger~anate(lI).
Under otherwise con~tant condit~on~ of tempera~ure, pre~
~ure and propylene-to-Pt ratios~ n-butyraldehyde wa~ ~he 2~ ~a~or hydroformylation product with each of ~he following cataly~t di~pers~o~.
27 ~Cl~H~tc0~s)9p~ 13~ - Pt~12[~(C~5)3]~ :
28l~n-c~)4N]~sn~l3] -29[(~Hs)~A~]tsn~l3~
30~(C7~ [S~Cl3~ 17 ~1~(c2Hs)~N~[Gecl3] - "
32~(~2Hs)4N]tSnCl33 - PtCl2~P(p~C~9~CeH~ 2 (c2H5)~N3[sn~l3] - P~Cl2[P(~-C4~)3~2 ~0 34[(C2Hs)~][SnCl3] PtCl2[P(CH~)2C~H5]2 ~25~
.: : . .
-' ' ' .' , ~ ~ ' :
TA:BLE V
PROPYI.~3NE HYDROFOR~YIATION CATAL~ZED BY
- E~IS fTRIP~IENYLPHOSPHINE ) PLATI~M (I~ DE
. J~ ..
Yle ld Puri ty o i~o lated of lso lated a ButyraldPhyde butyr~ldehyde~ butyraldehyd~
~, ~electivity (%) I_) (%~
8:2 ~8 99 .
_26 - ' , ~}~PTE~ 3~41 }~DROFOR~YIAlqION OF OL;E:TI~S CA~L~ZED BY
~ ~N STRUCTIJ~E
___ Table V~l: which follows, ~hows kh2 data obtalned when t~e de~ignated olefin3 ar~ hydrofo~ylated U~itlg the procedur~ of l3xample 1. All ~he exampl~ ~how~ in Ta~le VI were carrled out under ~he followlng cooditioTI~:
~olvent, methyl lsobutyl k~one Olefin, o.88 moles per lit~r . Ol~in/plat1num molar ratio, 200/1 5nClaJPtCl2 (PPh3 3 ;2 molar ratio, 5/ l /CO 3 1/17 1500 p~ig or 1260 p~ig Reactio~ temperature, 66C
R@ac~ion t~e, 3 6 ~ours (exclu~ive of 7IcooL down"
periods ~ .
The data in Table V:i: demonstrat~ th~t straight chain (linear) alpha-olefi~s are rea~ily hydroformyla~ed.
Brsnched chain -olei~ are le~ ea~ly hydroformylated~
ll~ternal s~d cyclic ole1n~ are the most dificult to hsrdroo~msrlata u~ng he catalysts of thi~ iLn~rerltion under ... . . .... . . ... . .......... ..
~ld reac'cion condl~ OTl~ O
EgAMPLE 4 2 __ .
PREPARATIC)N OF OXIDE-SUPPORTl~:D Ni/A.l/Cr CATALYST
~ , Sodiu~ bicarbona~ ~3?~) gm) i~ di~olved in 3 ll~ers of d:L~till~d wal:es aRd, the ss~lution heated ~o 80C,.
~ydra~ed nic~eel ni~rate (291 gm), hydrated aluminum nitrate ~J (1~7 g~ nd chromium ~:i tratP (4C) gm) are also dissolved i~
3 lit~rs of distill~d water, heated to ~30C, arld the hot nltrate solution slowly added to l:he hot Yodium bicarbonate 3o eolution. After stirring for 1 hour, the mix'cur~ is filtered and the solid~ wa~hed eight timex with 2 liters of .
~rl ~ ¦
rl h I r) 0~ O 1~ O ~1 .
O ~
1~ N Il ) N ~) C~ O
~: ~
,0 ~
O ~U ~ 0~~
h ~ ~) I o o Eo3 ~
~n o\o H N
rO '~
.r~ ~ I~ O~O ct,O ~
~ ~ r-~
~ r-l r~
U7rl q~ u, C~ r1 ~ O In ~ 1~ 00 ~D L(l HO ~r1 ~ a- 00 00Ll'l r-l N
~E~
~,Ll ~
i~ r~ 111 ~rl . r h I~ C~rN' N
r ~ ~ L~l ~ ~ ~,~
X ~rf ,S:~
h ~0 o o oo o o o ~ O ~O O o Ul U~ N 11'~N Lt') ~ N
h r~l r-l ~Ir-l r l H r-l C~
O O r~l ~ ~ C ~ ~ r-l ~ X
4~ r~ O O ,~ ~ ~ r~
a~ ~ p,, ~ P., o O h ~ r~l ~1 r~lN p ~ N ~_7 r~
~d ~--1 L~ ~D l~00 5 0 ~-1 ,r~
~ t) ~ d' Ul . ~
- . . " ,`:.` . .
lL
hot di~tilled water. The fil~rate o:f the last wa~h ooll-tained 20 ~) p~m ~odium. The ~ol~ ds are dried overnight at 110C:, calclned at 400C for 2 hvur3J and then preredllced under a oitrQgen/hydrogen purge ~t 325C.
_~ ~el~h~ of cataly~ prior ~o prereduction - 110 gm Ana l~si~: Ni - - 54 . 7%, Al - 11. 4%, Cr 4 . 72 Na ~ ppm ~MPI,E
__ PREPARATI~)N OF OXIDE-SllPPORl~D Ni/Ba/Cr CATALYST
Sod~ um carbonate ~5~; gm 3 ~s di~o lved irl two ll ters of di~tilled wa~er a~d the solu~clo~ hea~d to 80C. ~Iydrated nickel ~i~ra~e (~36 gm~, hydrated chro~ium ~itra~e (80 gm) nd barium nitra~e (1~7 gm) are also dls~olved ira 3 li ers of dls~illed wa~er., heat~d to 80C, and ~he ho~ nitrate ~olu~on Rlowly added to the hot odium carbo~a~e solu~ion.
~ter stirring or 1 hour at 80C, t}~e mi:1ctur~ is ~i~tered, arld the 301id8 wa9hed eighi~ time~ wlth 2 1it~r~ of hoe water. The solids are dried overnlg~9 calcined at 400C for 2 hour~, agld pr~r~duced ~n :a n1t~genlhydrog~n s~ream at 325C.
Weight of ca~ ly~t prior to prereduction - 243 gm ARalys i~: Ni - 32 . 6,~, Ba - 32 . :~, Cr 4 . 125~, ~a ~ O. 12 E~l~
___ 50dlum carbonate (?50 ~m) is dlssolved in three liter~ of distilled water arld the solution heated to 80C.
~Iydrated nickel nitrate (3~;0 gm), hydrated magnesium car-bonate (180 g) a~ld hydrated chromium nitrate (2~ gm) are dissolYed in 1.5 liters of di~tilled water, h2ated ~o 80C, and the ho~ nitrate ~olution slowly added to the hot ~odium ., ` ~ , .
carbonate solueiorl. After tirrlng a~ 85C ~or 1 hour, t~e mlxtur~ i~ filtered, and the ~olid~ washed ~igh~ times ~ith 2 li~rs o~ hot dis~illed water. Th~ f:iltr~te from the las~ wa~hlng contain~ 14 ppm Na. The solids are drled overnightJ calcin~d at 400C for 2 hours, aad preredueed in a ~re~m of ni~rog@n/hydrsgan a~c 325C.
Welght of aatalyst prior to prer~ductlon - 127 gm Ar~aly~ Ni - 51.1%, Mg ~ , Cr - 1~89%, Na - 695 ppm ~
REDUClIVE A2~N~ATION OF OCTYLALDE~YDES TO OCTYIAMINES
An appropriately 9i2ed autoclave re~c~or equlpped with heatillg, coolingg agita.ion9 pressurizirlg mean~, a side ~mpoule sy~te~ for ~Tlproducing charges Imder opera~cing condl~ , and a samp~ g valve, ls charged wi~h de-oxygenated methanol (100 ml). To the agita~ed 501vent under ~ nit~ogerl ~urge iLs added 10 ml of o~tylaldehydes, prepared according to the procedure of ~xa~ple 1 and con-taining 83 mole % n~octanol~ plu5 15 gm of oxide-suppor~ed ~ickel c~t . ly~t, prepared a eording to the procedure of Eæ~ple ~2. The r~action vessel i~ d~o~ygenated, 20 gm of ammor~ia lrl~ected ln from the ~ide ~poule, and ~he whole pre~surad to 1200 p~ig wi'ch hydrogen. ~he reac~ion ~nixture i~ then heated to 100C, with agitation, nd ~eld at temperature for 4 hours.
On cooling and venting, the liquid product is ~epara~ed from the solid catalyst by fil~ration and subjected ~o analysis by g2LS chr~matography. Octylamines, 30 9~ gm, 89~ n-octylamine, are i olated by fractional distillation.
fl~
Ga~ chroznatographic (~c ~ analg~ revealed ~he follow Ing re~ul~s:
Con~ersiorl of oc tql~ldehydes: a 985~
Yield o octs~lamine~: 48%
5eleeti~ty ~o n~octylamine: 89 E~IES 46~3 ,,~
REDUCTIVE ~fINAllO~ C)F VARIOUS AL~IAIDEHYDE5 T0 ~IAMINE5 GA~ALY~ED BY NICXEL~CONTAINING CATAl,YSTS
Table ~ hich follow~, ~hows ~h~ data obtained when ~he designated o~id~supported, n~ckel-contalnlng caltaly~ ts of ~chi~ vent~ on, pr~pared accordi~ to ~ha procedures o Exampl~ 42-4~, are scre~lled for th~ r~-duct~ve am:Lnation of Gs~Cl4.1inear al;kyl aldahyde~ to the~r corre~ponding lirlear C~c~alkyl primar~ e~ by the pro~
cedure of ~xampl~ 45. The para~finic aldehyde sub3trate3 ~nay be prapared by any of the proc~dure~ o Eæamples 1-41, but par~i6ularly ~hose ou~ ed i~ Ex~mple 1 uslng the h~ogeneou~ bi~tripherlylpho~ph~n~platirlum(II)-tin(II) chloride cataly~t9 ar~d Example 26, u~i~g the di~persioT~
uf b~(triphenylphn~phine~pla~lnum(~I~ chIor~de in t~ra-ethyla~oni~ ~richloro~tannate~II).
~ ~ay be noted fr~m the data in Table ~ that:
a~ C~-C~ ear prlmary ~min28 have bee~ pr~
pared by the proceduxe of Ex~mple 45 uslng all ~hree o~ide-supported ~ick~1containi~g cataly~ts deQcribed by Ex2mples 4~44.
~ ~m:Lnation is ach~ ved over a wide range of operating te~p~rature~ and presqur~s.
' c ) The oxide-supported9 nick~l containing cata-ly~ts remain ac~.L~e ollo~1~g reductive aminasionJ and may b~ recycled with additional linear parafinic aldehyde 2ed ~o produce addlt:Lonal de~ired n~alkyl pr~mary amine product imprvved yield~ (eg. 380 mole %, Example 523.
-3l- .
_~ ~ ~ l ~ ~ O ~ ~ ..
~o p~ ~;
~ 3 .~ u ~ ~ $
~ c e c:
a~--:~ .
~ C A ,~ A C~ 5 ~ a~
~1 0~ ~ O ~ O
QO ~ O ~ O 'O ~ t~
~1 ~ ~ ~ u~
Ei 0~ O ~ O ~ O
o~ CU ~ CU CU
o ~3 o ~a ~ -~ 0 9-l C,~ ~ ~ L~
' ~: ~ ~1 E~a~
C
., ~O
o ~ a~
~ C~ .
C: ~0 ~ p~
3 6~ ~:
~ ~.n I ~
Z ~ C~ J
.. C~
CL
~ ~ 0 X _~ ~ ~r ~ u~ ~ ~ L~
~3~-:.
E~PIE 54 ~..
OXOAMINATXON OF PROPYIENE C~TALYZED BY A COMBI~TION OF
BIS(TRIPHENYLPHOSPHINE) PIATIN~M~II) C~ORIDE-STANNOUS
CHLORIDE PLUS O~IDE~SUPPORTED NICKEL CATALYST
In this ex~mple the oxo~minatlon o pro~yl~ne to butylamine is carrled out i~ accordance wi~h the procedure o~ ExampXe LA ~ æ ept that the inltial ca~aly~t cha~e con~
~ist~ of a mi~tu~e of bi~(triphenylpho3phin~)pl~tinum(II) chloride (1.0 mmole3, t~(II) chlorlde (5.0 ~mol~, and oxide~
supported ~iekel ca~alyst (5 ~) prepared according to th~
procedure of Example 43. 5aid ca~alyst mix~ure is 3u~p~nded in 60 ~1 of tolu~ne, 8.~ g o propylene (200 ~mole) in~ct~d fr~m a side~mpoule9 and the hydroormylation to n~butyral~
dehyde carried out in accordance wi~b ~he co~di~ioa~ outli~ed i~ Ex~mple3 1 and LA. Gas chrama~o~raphic a~alys~s of the crude product liquid confinm~ the fo~ma~ion o n~bu~yralde-hyde in 9~% ~electi~ity.
The crude produc~ mixture i~ the~ treated with 30 ~1 of metha~ol, 10 g of ammonia i~ inj~cted frQm the ~de ampoule, and ~he reductive amination c~rried ou~ 1~ accord-snce w~th the proc~dur~ o~ Examples lA and 45. On cooli~g and v nti~g~ the l~quid product ~ separa~ed from ~he re-maining ~olid cataly~t by iltration and ~ub~ected ~o anaLy-8i~ by ~a3 chroma~ogr phy. nButylamine 1~ ob ai~2d in 95~ ~electivity and ~10 mole % yield basis C~H3 charged.
-33~
A~ the numerou~ exEmple~ o~ thi~ lnverltior indlcate, th~ subject inventivn i~ advantageou~ ln several r~spects co~par~d to corresporld:l ng o~o~irlation of ~he prios art. For e~ple, uslng variou3 platinu~IX) .' ligand ~tabiliz@d-~tar~nous chloride hydro~ormylatlon cataly3t complexe~, 1 alken~ can be hydro~ormylated o ald~hyde~ at r~la~vely mild reae~io~ eontition~ o~
temperature and pre~3ure. Furthermore, seleetivities to the l-aldehyde3 arP ge~erallg exce llent 9 and c~mpe ting isomerization and reduction reaction~3 are kept to a ~inimum. In ~ddi~io~, avorable (larg~ ~ ratios of alkene so catalyst may be empls:~yed and g~nerally mo~t polar ~o~Jents are sultabl~ a~ reactlon medla, L~kewi~e l:he var~ous oxide support~d ~ickel-co~tainlng amiRation cata~
ly~ts, ~escribed here~n~ exhlbit good pecific acti~ ty and selecti~rlty to li~ear alk~rl p~imary am~ne duriRg the reductive amination ~t~p, with l~aproved performanGe~ upon recycle .
Flnally, the invention is qu~ ~e advarl~ageous i~
that nu~rou3 subs titutions, modi~icat~ o~ and cha~ige~
can be mate without departing rom the inven~ive ~onc~pt.
~owe~er, the 8~:0pe o the ~ubject inve~tion csn b~st be u~derstood by ~xaminin8 the claim~ which follow, irl con junc~on with the preceding speci~lcatio~.
-34~
. .
As the data of l'a~le II indicate, meaa~n~f hydrofo~nyla~ion of l-heptene to octyl aldeh7de i~ ob tained under our preferred ~n:ild reaction cond~tlon~ whe a srariety of llgands containlng Group VB, YIB and VIIB
donor ato~ns ~re u~ed to ~tabillze the platlnum halide c~mplexe~ tog~ther with the ~anr~ou~ halide m~al salt~
~o fo~m a cataly~. The pref~rred ligand3 appear to be eho~e conta~ning; a trlval~nt pho~phoru~ dorlo~ a~
E~PI ES 19~25 io }~YDROFORMYIATION ()F l-HEPl~NE CATALYZED
PLAllN(~M BIMETALIIC COMPLEXES - EFFECT
OF TRIVALENT PH :)SPHO~OUS IIGANDS
Table IV which follow~ shows the data obtain~d when the d~signa~ed cataly~ts are employ~d in ~he hydro-formylation o~ l-h~ptene using the procedure o Ex~pl~ 1.
All the examples ~hc~n in Table IV were carried out under the conditions descr bed in Example 1 a~d Table I.
A~ the data of Ta~le IV ind:lc~e, meaningfu~
hyd~oormylation of l-hepeens to octyl aldehyde $3 ob-tai~ed u~der our pre~erred mild reactioTI co~di~lon whe~
a Yasiety of tr~alerlt organo-pho~phoraus ligands are u~ed ~o modify Pt(II) chloride ~ ~tannou~ chloxid~ cata~
ly8t30 These includ~ ..riaryl9 triallyl~ ~ubstituted triar~rl and mixed alh:yl, aryl pho~phin~30 Triaryl pho3 phites, such a~ triphenyl phosphite, are a~o suitable.
Complexeq with mixed ~ubstituted pho~phines, such a~
PC1(Ph)2J are active, as are csmplexes with biden~ate phosphines ~uch as Ph2PC~I2CH2PPh2.
b~ ~
~ ~ o cr rl h ~
~: ~
~ Q~
,~
~ O ~ ~ ~ rr), ~ ~
i~ ~
,1 o ~ ~
o ~ ~ ~n 1~ a~ oo a-Ul .~
H ~I
o~o ~ ~ ~
~rl.S 0 00 C~
~, ~ a I` 00 Ot~ O~ I` 00 a~ ~1 -~ ~d V~ ~
~ ~ Lr~
~ ~>.C oo E~
a) ~o o ~ o a~ o o ~ a~ _I ~ ~1 ~1 :r ~
I O
_~ ~ 5 N
~d ~ ~rl ~1 ~I r~
~n ~ ~ o ~ ~ ~ ~ ~ .
X ~ ~I c~ ~ N .
r l N~, U~ +
o ~ * ~
t~ ~ ~ ~1 N t,~ t~l r_ p., 3 ~ C ~ ~ ~ :
~ 0 td C~
L~ 4 ~1 N ~ N t`J t~ t`l C~ ~ ~ r-l :
~ ~ ~ ~ ~ ~ ~ ~d .. .
~d :
o ~ c~ ~7 ¦ ~ ~ ~ ~ ~ N ~
:.
E~PLE 26 HYDROFORMYLATION OF PROPYLENE C~TALYZED BY
BIS (TRI~NYL~IOSPEIINE ) PLATINUM (II ) C:HI.ORIDE
DISPERSED IN TE:TRAETHYLA~ONIUM TRICHLORO~
An appropriate ly ~ized react~on ve~sel~ ~uch ~` a~ an autoclave, equipped with he~ting, oo1illg, agitatir~g;
pressur1zing mean~, and a ~ide ampou1e 8y~tem for intro-ducing char~;e~ u~der operating cond1tions, is chaxged w~th a ~ample of tetra~thy1=o~iLum tr.lch10ro~taTmate (II~ (14. 2 g ~0 mmole) and bi~ ttripheny1phosphine)p1at1num(II) chlo~
ride (:~S.16 g 4.0 mmole). The reactor sealed, purged with CO, a~d pres~ured to 1260 p~ig with 42 g o propylene (} mole) plu~ a 1:1 (Y/V) ~a~ mixtu~e o~ C/E12~ The mixture i~ heate~ to 80C, stirre~ for 5 hours at temperature~ and allowed to cool. Forty gram~ o~ y~llow liquid prGduct are recovered by decaDt~on ro~ he y llow cry~talline melt, and fract:T.onally di~tilled. Butgraldehyde~ (34.5 g 0.~ mole) are recovered from a fraction boiling 72-75C (l atm), and al~alyzed by ga~ chromatography usirlg a 10 t ~ 1/4'l colum~
of 20,~ OS-l 4 on chromasorb "G" heated ~o 1 0G with 100 cc/
min. P,le flow.
Yle ld o~ iso lated butyraldehyde~ 34 . 5 gram~
Yield of ~.~olal:~d butyraldehydes (ba3is propylene charged) 48 ~ole %
Purity of i~olated butyraldehydes 99~;
Se lec tivi ty to n -bu~yraldehyde 82~
- The rPcovered cry~talline melt cataly~t remains an active hydrofor~rlation catalyst aft~r butyraldehyde re-covery by decaneation. Additional ~butyrald2hyde may be p~eepared simply by recycIing the used dispersioll of platinum catalyst in quaternary alkyl trichlorostannate(II~ salt with -2~-fre~h propylene under the hydrofor~yla~ion condi~lon~ de~
~crlber ~E~ Yield data or the isol~ed butyr~ld~hyde3 prepared over a three cycL~ experiment using the ~m~ sample of bis(triphenylpho~phine~platin~m(lI) chlorlde disper~ed in etraethylam~onium trichloroqtannata~II) ar~ ~um~a~ized in Ta~l V.
~MPLES ~7-34 __ ~YDR~FO~MYLATIO~ OF PROPYL~ C~TALYZED BY
II~A~D-S~ABIIIZ~D PLATINUM(II) C~MP~EXES DISPERSED
I~ VARIOUS QUATERNARY 8ALTS OF ~RIC~ROS~A~N~TE(II) AND TRIC~IDROOERMANA~(II) __ In the~e examples the hydro~oxmylat~on of propyl~
ene to n-buty~aldehyde ~ carrled o~t in accordance ~ith the procedure of Example 26, but in the presence o~ vsriou~
liga~d s~abilizgd pl tinum(II) c~mplexe~ d~persed in a uumb~r of ~uaternary ~mmonium, pho3phonium and arsolllum ~alt~ of trlhalostannatetII) a~d trihaloger~anate(lI).
Under otherwise con~tant condit~on~ of tempera~ure, pre~
~ure and propylene-to-Pt ratios~ n-butyraldehyde wa~ ~he 2~ ~a~or hydroformylation product with each of ~he following cataly~t di~pers~o~.
27 ~Cl~H~tc0~s)9p~ 13~ - Pt~12[~(C~5)3]~ :
28l~n-c~)4N]~sn~l3] -29[(~Hs)~A~]tsn~l3~
30~(C7~ [S~Cl3~ 17 ~1~(c2Hs)~N~[Gecl3] - "
32~(~2Hs)4N]tSnCl33 - PtCl2~P(p~C~9~CeH~ 2 (c2H5)~N3[sn~l3] - P~Cl2[P(~-C4~)3~2 ~0 34[(C2Hs)~][SnCl3] PtCl2[P(CH~)2C~H5]2 ~25~
.: : . .
-' ' ' .' , ~ ~ ' :
TA:BLE V
PROPYI.~3NE HYDROFOR~YIATION CATAL~ZED BY
- E~IS fTRIP~IENYLPHOSPHINE ) PLATI~M (I~ DE
. J~ ..
Yle ld Puri ty o i~o lated of lso lated a ButyraldPhyde butyr~ldehyde~ butyraldehyd~
~, ~electivity (%) I_) (%~
8:2 ~8 99 .
_26 - ' , ~}~PTE~ 3~41 }~DROFOR~YIAlqION OF OL;E:TI~S CA~L~ZED BY
~ ~N STRUCTIJ~E
___ Table V~l: which follows, ~hows kh2 data obtalned when t~e de~ignated olefin3 ar~ hydrofo~ylated U~itlg the procedur~ of l3xample 1. All ~he exampl~ ~how~ in Ta~le VI were carrled out under ~he followlng cooditioTI~:
~olvent, methyl lsobutyl k~one Olefin, o.88 moles per lit~r . Ol~in/plat1num molar ratio, 200/1 5nClaJPtCl2 (PPh3 3 ;2 molar ratio, 5/ l /CO 3 1/17 1500 p~ig or 1260 p~ig Reactio~ temperature, 66C
R@ac~ion t~e, 3 6 ~ours (exclu~ive of 7IcooL down"
periods ~ .
The data in Table V:i: demonstrat~ th~t straight chain (linear) alpha-olefi~s are rea~ily hydroformyla~ed.
Brsnched chain -olei~ are le~ ea~ly hydroformylated~
ll~ternal s~d cyclic ole1n~ are the most dificult to hsrdroo~msrlata u~ng he catalysts of thi~ iLn~rerltion under ... . . .... . . ... . .......... ..
~ld reac'cion condl~ OTl~ O
EgAMPLE 4 2 __ .
PREPARATIC)N OF OXIDE-SUPPORTl~:D Ni/A.l/Cr CATALYST
~ , Sodiu~ bicarbona~ ~3?~) gm) i~ di~olved in 3 ll~ers of d:L~till~d wal:es aRd, the ss~lution heated ~o 80C,.
~ydra~ed nic~eel ni~rate (291 gm), hydrated aluminum nitrate ~J (1~7 g~ nd chromium ~:i tratP (4C) gm) are also dissolved i~
3 lit~rs of distill~d water, heated to ~30C, arld the hot nltrate solution slowly added to l:he hot Yodium bicarbonate 3o eolution. After stirring for 1 hour, the mix'cur~ is filtered and the solid~ wa~hed eight timex with 2 liters of .
~rl ~ ¦
rl h I r) 0~ O 1~ O ~1 .
O ~
1~ N Il ) N ~) C~ O
~: ~
,0 ~
O ~U ~ 0~~
h ~ ~) I o o Eo3 ~
~n o\o H N
rO '~
.r~ ~ I~ O~O ct,O ~
~ ~ r-~
~ r-l r~
U7rl q~ u, C~ r1 ~ O In ~ 1~ 00 ~D L(l HO ~r1 ~ a- 00 00Ll'l r-l N
~E~
~,Ll ~
i~ r~ 111 ~rl . r h I~ C~rN' N
r ~ ~ L~l ~ ~ ~,~
X ~rf ,S:~
h ~0 o o oo o o o ~ O ~O O o Ul U~ N 11'~N Lt') ~ N
h r~l r-l ~Ir-l r l H r-l C~
O O r~l ~ ~ C ~ ~ r-l ~ X
4~ r~ O O ,~ ~ ~ r~
a~ ~ p,, ~ P., o O h ~ r~l ~1 r~lN p ~ N ~_7 r~
~d ~--1 L~ ~D l~00 5 0 ~-1 ,r~
~ t) ~ d' Ul . ~
- . . " ,`:.` . .
lL
hot di~tilled water. The fil~rate o:f the last wa~h ooll-tained 20 ~) p~m ~odium. The ~ol~ ds are dried overnight at 110C:, calclned at 400C for 2 hvur3J and then preredllced under a oitrQgen/hydrogen purge ~t 325C.
_~ ~el~h~ of cataly~ prior ~o prereduction - 110 gm Ana l~si~: Ni - - 54 . 7%, Al - 11. 4%, Cr 4 . 72 Na ~ ppm ~MPI,E
__ PREPARATI~)N OF OXIDE-SllPPORl~D Ni/Ba/Cr CATALYST
Sod~ um carbonate ~5~; gm 3 ~s di~o lved irl two ll ters of di~tilled wa~er a~d the solu~clo~ hea~d to 80C. ~Iydrated nickel ~i~ra~e (~36 gm~, hydrated chro~ium ~itra~e (80 gm) nd barium nitra~e (1~7 gm) are also dls~olved ira 3 li ers of dls~illed wa~er., heat~d to 80C, and ~he ho~ nitrate ~olu~on Rlowly added to the hot odium carbo~a~e solu~ion.
~ter stirring or 1 hour at 80C, t}~e mi:1ctur~ is ~i~tered, arld the 301id8 wa9hed eighi~ time~ wlth 2 1it~r~ of hoe water. The solids are dried overnlg~9 calcined at 400C for 2 hour~, agld pr~r~duced ~n :a n1t~genlhydrog~n s~ream at 325C.
Weight of ca~ ly~t prior to prereduction - 243 gm ARalys i~: Ni - 32 . 6,~, Ba - 32 . :~, Cr 4 . 125~, ~a ~ O. 12 E~l~
___ 50dlum carbonate (?50 ~m) is dlssolved in three liter~ of distilled water arld the solution heated to 80C.
~Iydrated nickel nitrate (3~;0 gm), hydrated magnesium car-bonate (180 g) a~ld hydrated chromium nitrate (2~ gm) are dissolYed in 1.5 liters of di~tilled water, h2ated ~o 80C, and the ho~ nitrate ~olution slowly added to the hot ~odium ., ` ~ , .
carbonate solueiorl. After tirrlng a~ 85C ~or 1 hour, t~e mlxtur~ i~ filtered, and the ~olid~ washed ~igh~ times ~ith 2 li~rs o~ hot dis~illed water. Th~ f:iltr~te from the las~ wa~hlng contain~ 14 ppm Na. The solids are drled overnightJ calcin~d at 400C for 2 hours, aad preredueed in a ~re~m of ni~rog@n/hydrsgan a~c 325C.
Welght of aatalyst prior to prer~ductlon - 127 gm Ar~aly~ Ni - 51.1%, Mg ~ , Cr - 1~89%, Na - 695 ppm ~
REDUClIVE A2~N~ATION OF OCTYLALDE~YDES TO OCTYIAMINES
An appropriately 9i2ed autoclave re~c~or equlpped with heatillg, coolingg agita.ion9 pressurizirlg mean~, a side ~mpoule sy~te~ for ~Tlproducing charges Imder opera~cing condl~ , and a samp~ g valve, ls charged wi~h de-oxygenated methanol (100 ml). To the agita~ed 501vent under ~ nit~ogerl ~urge iLs added 10 ml of o~tylaldehydes, prepared according to the procedure of ~xa~ple 1 and con-taining 83 mole % n~octanol~ plu5 15 gm of oxide-suppor~ed ~ickel c~t . ly~t, prepared a eording to the procedure of Eæ~ple ~2. The r~action vessel i~ d~o~ygenated, 20 gm of ammor~ia lrl~ected ln from the ~ide ~poule, and ~he whole pre~surad to 1200 p~ig wi'ch hydrogen. ~he reac~ion ~nixture i~ then heated to 100C, with agitation, nd ~eld at temperature for 4 hours.
On cooling and venting, the liquid product is ~epara~ed from the solid catalyst by fil~ration and subjected ~o analysis by g2LS chr~matography. Octylamines, 30 9~ gm, 89~ n-octylamine, are i olated by fractional distillation.
fl~
Ga~ chroznatographic (~c ~ analg~ revealed ~he follow Ing re~ul~s:
Con~ersiorl of oc tql~ldehydes: a 985~
Yield o octs~lamine~: 48%
5eleeti~ty ~o n~octylamine: 89 E~IES 46~3 ,,~
REDUCTIVE ~fINAllO~ C)F VARIOUS AL~IAIDEHYDE5 T0 ~IAMINE5 GA~ALY~ED BY NICXEL~CONTAINING CATAl,YSTS
Table ~ hich follow~, ~hows ~h~ data obtained when ~he designated o~id~supported, n~ckel-contalnlng caltaly~ ts of ~chi~ vent~ on, pr~pared accordi~ to ~ha procedures o Exampl~ 42-4~, are scre~lled for th~ r~-duct~ve am:Lnation of Gs~Cl4.1inear al;kyl aldahyde~ to the~r corre~ponding lirlear C~c~alkyl primar~ e~ by the pro~
cedure of ~xampl~ 45. The para~finic aldehyde sub3trate3 ~nay be prapared by any of the proc~dure~ o Eæamples 1-41, but par~i6ularly ~hose ou~ ed i~ Ex~mple 1 uslng the h~ogeneou~ bi~tripherlylpho~ph~n~platirlum(II)-tin(II) chloride cataly~t9 ar~d Example 26, u~i~g the di~persioT~
uf b~(triphenylphn~phine~pla~lnum(~I~ chIor~de in t~ra-ethyla~oni~ ~richloro~tannate~II).
~ ~ay be noted fr~m the data in Table ~ that:
a~ C~-C~ ear prlmary ~min28 have bee~ pr~
pared by the proceduxe of Ex~mple 45 uslng all ~hree o~ide-supported ~ick~1containi~g cataly~ts deQcribed by Ex2mples 4~44.
~ ~m:Lnation is ach~ ved over a wide range of operating te~p~rature~ and presqur~s.
' c ) The oxide-supported9 nick~l containing cata-ly~ts remain ac~.L~e ollo~1~g reductive aminasionJ and may b~ recycled with additional linear parafinic aldehyde 2ed ~o produce addlt:Lonal de~ired n~alkyl pr~mary amine product imprvved yield~ (eg. 380 mole %, Example 523.
-3l- .
_~ ~ ~ l ~ ~ O ~ ~ ..
~o p~ ~;
~ 3 .~ u ~ ~ $
~ c e c:
a~--:~ .
~ C A ,~ A C~ 5 ~ a~
~1 0~ ~ O ~ O
QO ~ O ~ O 'O ~ t~
~1 ~ ~ ~ u~
Ei 0~ O ~ O ~ O
o~ CU ~ CU CU
o ~3 o ~a ~ -~ 0 9-l C,~ ~ ~ L~
' ~: ~ ~1 E~a~
C
., ~O
o ~ a~
~ C~ .
C: ~0 ~ p~
3 6~ ~:
~ ~.n I ~
Z ~ C~ J
.. C~
CL
~ ~ 0 X _~ ~ ~r ~ u~ ~ ~ L~
~3~-:.
E~PIE 54 ~..
OXOAMINATXON OF PROPYIENE C~TALYZED BY A COMBI~TION OF
BIS(TRIPHENYLPHOSPHINE) PIATIN~M~II) C~ORIDE-STANNOUS
CHLORIDE PLUS O~IDE~SUPPORTED NICKEL CATALYST
In this ex~mple the oxo~minatlon o pro~yl~ne to butylamine is carrled out i~ accordance wi~h the procedure o~ ExampXe LA ~ æ ept that the inltial ca~aly~t cha~e con~
~ist~ of a mi~tu~e of bi~(triphenylpho3phin~)pl~tinum(II) chloride (1.0 mmole3, t~(II) chlorlde (5.0 ~mol~, and oxide~
supported ~iekel ca~alyst (5 ~) prepared according to th~
procedure of Example 43. 5aid ca~alyst mix~ure is 3u~p~nded in 60 ~1 of tolu~ne, 8.~ g o propylene (200 ~mole) in~ct~d fr~m a side~mpoule9 and the hydroormylation to n~butyral~
dehyde carried out in accordance wi~b ~he co~di~ioa~ outli~ed i~ Ex~mple3 1 and LA. Gas chrama~o~raphic a~alys~s of the crude product liquid confinm~ the fo~ma~ion o n~bu~yralde-hyde in 9~% ~electi~ity.
The crude produc~ mixture i~ the~ treated with 30 ~1 of metha~ol, 10 g of ammonia i~ inj~cted frQm the ~de ampoule, and ~he reductive amination c~rried ou~ 1~ accord-snce w~th the proc~dur~ o~ Examples lA and 45. On cooli~g and v nti~g~ the l~quid product ~ separa~ed from ~he re-maining ~olid cataly~t by iltration and ~ub~ected ~o anaLy-8i~ by ~a3 chroma~ogr phy. nButylamine 1~ ob ai~2d in 95~ ~electivity and ~10 mole % yield basis C~H3 charged.
-33~
A~ the numerou~ exEmple~ o~ thi~ lnverltior indlcate, th~ subject inventivn i~ advantageou~ ln several r~spects co~par~d to corresporld:l ng o~o~irlation of ~he prios art. For e~ple, uslng variou3 platinu~IX) .' ligand ~tabiliz@d-~tar~nous chloride hydro~ormylatlon cataly3t complexe~, 1 alken~ can be hydro~ormylated o ald~hyde~ at r~la~vely mild reae~io~ eontition~ o~
temperature and pre~3ure. Furthermore, seleetivities to the l-aldehyde3 arP ge~erallg exce llent 9 and c~mpe ting isomerization and reduction reaction~3 are kept to a ~inimum. In ~ddi~io~, avorable (larg~ ~ ratios of alkene so catalyst may be empls:~yed and g~nerally mo~t polar ~o~Jents are sultabl~ a~ reactlon medla, L~kewi~e l:he var~ous oxide support~d ~ickel-co~tainlng amiRation cata~
ly~ts, ~escribed here~n~ exhlbit good pecific acti~ ty and selecti~rlty to li~ear alk~rl p~imary am~ne duriRg the reductive amination ~t~p, with l~aproved performanGe~ upon recycle .
Flnally, the invention is qu~ ~e advarl~ageous i~
that nu~rou3 subs titutions, modi~icat~ o~ and cha~ige~
can be mate without departing rom the inven~ive ~onc~pt.
~owe~er, the 8~:0pe o the ~ubject inve~tion csn b~st be u~derstood by ~xaminin8 the claim~ which follow, irl con junc~on with the preceding speci~lcatio~.
-34~
. .
Claims (8)
1. A process for preparing linear alkyl primary amines by the catalytic oxoamination of linear alpha olefin substrates containing 2 to 30 carbon atoms, by the steps of first producing primarily linear aldehydes then preparing primarily the corresponding amines, by the steps of:
a) forming a hydroformylation reaction mixture of olefin substrate, carbon monoxide, hydrogen and from about 0.001 to 0.1 moles of a three-component, ligand-stabilized, platinum(II) halide catalysts per mole of ole-fin substrate, said catalysts being selected from the group consisting of:
PtC12[P(C6H5)3]2+SnC12 PtC12[P(p-CH3.C6H4)3]2+SnC12 PtC12[P(n-C4H3)3]2+SnC12 PtC12[P(C6H5)3]2+SnC14 PtC12[P(C6H5)3]2+GeC12 PtC12[P(CH3)2C6H5]2+SnC12 PtC12[Ph2AsCH2CH2AsPh2]+SnC12 PtC12[P(OC6H5)3]2+SnC12 PtC12[As(C6H5)3]2+SnC12 PtC12[S(C6H5)2]2+SnC12 PtBr2[P(C6H5)3]2+SnBr2 PtC12[Ph2PCH2CH2PPH2]+SnC12 PtC12[Sb(C6H5)3]2+SnC12 PtC12(o-Phenanthroline)+SnC12 PtC12[P(C6H5)3]2+(C13Sn][N(C2H5)4]
" +(C13Sn][P(C6H5)CH2C1]
" +[C13Sn][N(n-C4H3)4]
" +[C13Sn][As(C6H5)4]
" +[C13Sn][N(C7H15)4]
PtC12[P(C6H5)3]2+[C13Ge][N(C2H5)4]
PtC12[P(p-CH3.C6H4)3]2+[C13Sn][N)C2H5)4]
PtC12[P(n-C4H9)3]2+[C13Sn][N(C2H5)4]
the carbon monoxide and hydrogen being present in quantities sufficient to satisfy the stoichiometry of the hydroformyla-tion reaction, b) pressurizing the hydroformylation reaction mixture between about 100 psig to about 3000 psig and heating the pressurized reaction mixture at about 25°C to about 125°C
until a major amount of linear alkyl primary aldehyde prod-ucts and a minor amount of non-linear alkyl aldehyde products are formed, and c) contacting said linear alkyl aldehyde products with at least sufficient hydrogen an ammonia to satisfy the stoichiometry of reducing the linear alkyl aldehyde to linear alkyl primary amine product, pressurizing between about 100 psig to about 3000 psig and heating said linear alkyl alde-hyde from about 25° to about 200°C in the presence of a cat-alyst consisting essentially of oxide-supported nickel cat-alyst containing from 5% up to 75 weight % nickel in addition to two or more other metals selected from the group consisting of magnesium, barium, aluminum and chromium, until a major quantity of linear alkyl primary amine product is formed, and d) isolating the linear alkyl primary amine prod-uct contained therein.
a) forming a hydroformylation reaction mixture of olefin substrate, carbon monoxide, hydrogen and from about 0.001 to 0.1 moles of a three-component, ligand-stabilized, platinum(II) halide catalysts per mole of ole-fin substrate, said catalysts being selected from the group consisting of:
PtC12[P(C6H5)3]2+SnC12 PtC12[P(p-CH3.C6H4)3]2+SnC12 PtC12[P(n-C4H3)3]2+SnC12 PtC12[P(C6H5)3]2+SnC14 PtC12[P(C6H5)3]2+GeC12 PtC12[P(CH3)2C6H5]2+SnC12 PtC12[Ph2AsCH2CH2AsPh2]+SnC12 PtC12[P(OC6H5)3]2+SnC12 PtC12[As(C6H5)3]2+SnC12 PtC12[S(C6H5)2]2+SnC12 PtBr2[P(C6H5)3]2+SnBr2 PtC12[Ph2PCH2CH2PPH2]+SnC12 PtC12[Sb(C6H5)3]2+SnC12 PtC12(o-Phenanthroline)+SnC12 PtC12[P(C6H5)3]2+(C13Sn][N(C2H5)4]
" +(C13Sn][P(C6H5)CH2C1]
" +[C13Sn][N(n-C4H3)4]
" +[C13Sn][As(C6H5)4]
" +[C13Sn][N(C7H15)4]
PtC12[P(C6H5)3]2+[C13Ge][N(C2H5)4]
PtC12[P(p-CH3.C6H4)3]2+[C13Sn][N)C2H5)4]
PtC12[P(n-C4H9)3]2+[C13Sn][N(C2H5)4]
the carbon monoxide and hydrogen being present in quantities sufficient to satisfy the stoichiometry of the hydroformyla-tion reaction, b) pressurizing the hydroformylation reaction mixture between about 100 psig to about 3000 psig and heating the pressurized reaction mixture at about 25°C to about 125°C
until a major amount of linear alkyl primary aldehyde prod-ucts and a minor amount of non-linear alkyl aldehyde products are formed, and c) contacting said linear alkyl aldehyde products with at least sufficient hydrogen an ammonia to satisfy the stoichiometry of reducing the linear alkyl aldehyde to linear alkyl primary amine product, pressurizing between about 100 psig to about 3000 psig and heating said linear alkyl alde-hyde from about 25° to about 200°C in the presence of a cat-alyst consisting essentially of oxide-supported nickel cat-alyst containing from 5% up to 75 weight % nickel in addition to two or more other metals selected from the group consisting of magnesium, barium, aluminum and chromium, until a major quantity of linear alkyl primary amine product is formed, and d) isolating the linear alkyl primary amine prod-uct contained therein.
2. The process of Claim 1 wherein the three-component, ligand-stabilized. platinum(II) halide catalyst and the oxide-supported nickel catalyst are added to the reaction mixture prior to the aldehyde forming reaction and are present during both the conversion of olefin substrates to alkyl aldehyde products and during the amination of said aldehydes to linear alkyl primary amines.
3. The process of Claim 1 wherein the platinum hydroformylation catalyst consists of a dispersion of ligand-stabilized platinum(II) halide complex in a low-melting quaternary alkyl ammonium salt of trichlorostannate(II).
4. The process of Claim 1 wherein the platinum hydroformylation catalyst consists of a dispersion of bis(triphenylphosphine)platinum(II) chloride in tetra-ethylammonium trichlorostannate(II).
5. The process of Claim 1 wherein the linear aldehyde synthesis is carried out in the presence of an inert solvent.
6. The process of Claim 1 wherein the reductive amination step to produce linear alkyl primary amines is carried out in the presence of an inert solvent.
7. The process of Claim 5 wherein the inert solvent is selected from the group of solvents consisting of acetone, methyl ether ketone, methyl isopropyl ketone, acetophenone, benzene and toluene.
8. The process of Claim 6 wherein the inert solvent is selected from the group of solvents consisting of methanol, ethanol, isopropanol and tert. butanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77881777A | 1977-03-17 | 1977-03-17 | |
| US778,817 | 1977-03-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1114401A true CA1114401A (en) | 1981-12-15 |
Family
ID=25114474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA297,954A Expired CA1114401A (en) | 1977-03-17 | 1978-03-01 | Selective oxoamination process |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS53116307A (en) |
| BR (1) | BR7801571A (en) |
| CA (1) | CA1114401A (en) |
| DE (1) | DE2811403A1 (en) |
| GB (1) | GB1575481A (en) |
| YU (1) | YU65178A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8519425D0 (en) * | 1985-08-01 | 1985-09-04 | Ici Plc | Amine production |
| DE102010045142B4 (en) * | 2010-09-11 | 2013-02-21 | Oxea Gmbh | Process for preparing primary aliphatic amines from aldehydes |
-
1978
- 1978-01-30 GB GB3602/78A patent/GB1575481A/en not_active Expired
- 1978-02-09 JP JP1305778A patent/JPS53116307A/en active Pending
- 1978-03-01 CA CA297,954A patent/CA1114401A/en not_active Expired
- 1978-03-15 BR BR7801571A patent/BR7801571A/en unknown
- 1978-03-16 DE DE19782811403 patent/DE2811403A1/en not_active Withdrawn
- 1978-03-17 YU YU00651/78A patent/YU65178A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1575481A (en) | 1980-09-24 |
| YU65178A (en) | 1982-06-30 |
| BR7801571A (en) | 1978-11-28 |
| JPS53116307A (en) | 1978-10-11 |
| DE2811403A1 (en) | 1978-09-21 |
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