CA1066722A - Two-step method for hydrolyzing and hydrogenating acetal-aldehydes - Google Patents
Two-step method for hydrolyzing and hydrogenating acetal-aldehydesInfo
- Publication number
- CA1066722A CA1066722A CA232,645A CA232645A CA1066722A CA 1066722 A CA1066722 A CA 1066722A CA 232645 A CA232645 A CA 232645A CA 1066722 A CA1066722 A CA 1066722A
- Authority
- CA
- Canada
- Prior art keywords
- acetal
- improvement
- hydrogen
- hydrogenation
- cyclic acetal
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
ABSTRACT OF THE DISCLOSURE
A two-step method is provided for preparing polyols from compounds containing one six-membered acetal ring and one aldehyde functional group wherein the acetal is first hydrogenated in the presence of a hydrogenation catalyst and then hydrolyzed and hydrogenated in the pres-ence of a water insoluble strongly acid ion exchange resin and a hydrogenation catalyst.
A two-step method is provided for preparing polyols from compounds containing one six-membered acetal ring and one aldehyde functional group wherein the acetal is first hydrogenated in the presence of a hydrogenation catalyst and then hydrolyzed and hydrogenated in the pres-ence of a water insoluble strongly acid ion exchange resin and a hydrogenation catalyst.
Description
This invention relates to a two step proce~
~or preparing polyols rrOm cyclic acetal-aldehyde com-pounds.
Processes ~or the production o~ alcohols ~rom acetals have been disclosed heretorore in the art. For e~ample~ U.S, patent 2,888,492 issued May 26, 1959 to Fischer et al. discloses the conversion o~ an ethylenic aldehydo into a polyol having a carbinol gXouP in place Or the carbonyl group and containing a hydroxyl group linked to at least ono Or the carbon atoms Or the ethylenic group Or the starting aldehyd~ by acctal rormatlon, weak acid hydrolysis and hydrogenation.
In the proces~ Or this invention, howover, organic compounds eontaining one si~-membered acetal ring and one aldehyde group are ~irst .:
hydrogenat~d st sn elevated temperature in the presence Or , a catalytic amount o~ a hydrogenation catalyst to prepar~ -the corrosponding acetal-alcohol ~hich i~ then simultaneously hydrolyz~d and hydrogenated ln an aqueo w medium in th~
presence o~ hydrog~n and a hydrolytic a~unt o~ a strongly acid water lnsoluble ion e~change resin and a catalytic amount o~ a hydrogenation catalyst to ~orm the corre~ponding polyol8. I~ desired, the hydroly~is-hydrogenatiQn reaction may be al'o~ed to continu~ beyond the ~ormation o~ the ,i . .
~ polyol to achie~c cyclization o~ any polyols ~ormed which i are capable o~ cyclizing in the presence of a strong~aci~
~u¢h a~, ~or e~ample, the cyclization o~ 1,4-butanediol (BAD) to tetrahydrofuran (THF). -Th~ proce~ of this in~ention i~ illu~trated by the follo~ing reaction ~equence u~ing 2(3'-propanal)-5-methyl dlo2ane (PND) a~ a representatlve example Or the
~or preparing polyols rrOm cyclic acetal-aldehyde com-pounds.
Processes ~or the production o~ alcohols ~rom acetals have been disclosed heretorore in the art. For e~ample~ U.S, patent 2,888,492 issued May 26, 1959 to Fischer et al. discloses the conversion o~ an ethylenic aldehydo into a polyol having a carbinol gXouP in place Or the carbonyl group and containing a hydroxyl group linked to at least ono Or the carbon atoms Or the ethylenic group Or the starting aldehyd~ by acctal rormatlon, weak acid hydrolysis and hydrogenation.
In the proces~ Or this invention, howover, organic compounds eontaining one si~-membered acetal ring and one aldehyde group are ~irst .:
hydrogenat~d st sn elevated temperature in the presence Or , a catalytic amount o~ a hydrogenation catalyst to prepar~ -the corrosponding acetal-alcohol ~hich i~ then simultaneously hydrolyz~d and hydrogenated ln an aqueo w medium in th~
presence o~ hydrog~n and a hydrolytic a~unt o~ a strongly acid water lnsoluble ion e~change resin and a catalytic amount o~ a hydrogenation catalyst to ~orm the corre~ponding polyol8. I~ desired, the hydroly~is-hydrogenatiQn reaction may be al'o~ed to continu~ beyond the ~ormation o~ the ,i . .
~ polyol to achie~c cyclization o~ any polyols ~ormed which i are capable o~ cyclizing in the presence of a strong~aci~
~u¢h a~, ~or e~ample, the cyclization o~ 1,4-butanediol (BAD) to tetrahydrofuran (THF). -Th~ proce~ of this in~ention i~ illu~trated by the follo~ing reaction ~equence u~ing 2(3'-propanal)-5-methyl dlo2ane (PND) a~ a representatlve example Or the
- 2 -'' ~ ,' .
cyclic acetal aldehudes de~cribed herein:
o ~O~CH
I H-C-CH2-CH2-C~ -C~ CH-C ~ + ~ Hydrogenation \ ~ Catalyst 0~ ~ ~CH
C ~ -C~ -C~ -CH / CH-C~
O,_ OH
II C ~ -C~ -C ~ -C~CH-CH~ Ion E~chan~o Re61n / ~ Hydrogenat~on Catalyst~
O--CH
HO-C ~ -CH-C ~ -OH + ~O(CH~)40H
. CH3 ~~ and, optionally, ` H2f--~ :
III HO(C ~)~oH Ion e~change resi~ ~ C~ ~CH2 + ~ O
.
,~ .
The practlce o~ thi~ i~vention preclude~ the formatlon of in~oluble blsacetal~ ~hich cause louer yleld~ ~
ln a one-step hydroly~is-hydrogenation reaction. In a one-~tep reactlon, bisacetal Pormation eompete~ Nith the .~' hydrog~nation oP ~ree aldehyde ~hich occur8 too ~lo~ly to obviat~ the ~ormatlon of th~ bi~acetal. Bl~a~etal~ Porm by reaction Or free 1,3-diol ~ith the star.tin~ alaehyde- ..
.~ ac~tal as illustrated belo~, again uslng PMD as an ex~mple~
;~ . . .
',''~ '-
cyclic acetal aldehudes de~cribed herein:
o ~O~CH
I H-C-CH2-CH2-C~ -C~ CH-C ~ + ~ Hydrogenation \ ~ Catalyst 0~ ~ ~CH
C ~ -C~ -C~ -CH / CH-C~
O,_ OH
II C ~ -C~ -C ~ -C~CH-CH~ Ion E~chan~o Re61n / ~ Hydrogenat~on Catalyst~
O--CH
HO-C ~ -CH-C ~ -OH + ~O(CH~)40H
. CH3 ~~ and, optionally, ` H2f--~ :
III HO(C ~)~oH Ion e~change resi~ ~ C~ ~CH2 + ~ O
.
,~ .
The practlce o~ thi~ i~vention preclude~ the formatlon of in~oluble blsacetal~ ~hich cause louer yleld~ ~
ln a one-step hydroly~is-hydrogenation reaction. In a one-~tep reactlon, bisacetal Pormation eompete~ Nith the .~' hydrog~nation oP ~ree aldehyde ~hich occur8 too ~lo~ly to obviat~ the ~ormatlon of th~ bi~acetal. Bl~a~etal~ Porm by reaction Or free 1,3-diol ~ith the star.tin~ alaehyde- ..
.~ ac~tal as illustrated belo~, again uslng PMD as an ex~mple~
;~ . . .
',''~ '-
-3-.. ~
.
. .
~0667Z2 C~3 / CH2 \ / C~ ~H+]
C~ -CH ~ CH-C ~ -C ~ -CHO ~ C ~ ~ H ?
.~ CH2 - 0~ OH ~~~
~ Q~ /o -'C}~
3-CH / CH-CH2-C~ -CH ~ / CH-C
The bisacet~ls tend to bc insoluble, partieularly at tempera-ture~ lo~or than th~ir ~ormation tomperature, and, as a re-sult, they precipitate out durlng operation Or the process.
Particularly in continuo w co~mercial operatlon~, the amount ~ .... ..
Or precipitat0 ~hich settles out a~ter several cycle~ can be slgni~lcant enough to cause the equipment to bocome ~: plugged, nccos~itating ~hut-do~n, clean-ou~ and a ne~
start-up. It wa8 completely unexpected, howeYer, that pre-hydrogenation o~ the cyclic acetal-aldehyde could ~olve ; this problem ~thout creating an evon greator di~iculty since it i8 ~ell kno~n that acetal gro~ps ~orm ether linkagos on hydrogenation a~ see, Por example, Re~ctions Hydrogen ~lth Or~anic Compounds over Copper, Chromium O~ido and Nlc~el Catalyst~ by Homer Adkins, P. 75. Si~ce the eth~r llnkage i8 stablo to hydrolysi~, it ~ould be ~; expected that prohydrogenatien ~ould dereat the goal Or thl~
~nvention. Contrary to this expectation it ha6 been ~ound th~t polyol8 can be easily and e~Piciently prepared w~thout the Pormation oP bisacetals and ~ithout the P~rm~tlon o~ :
ether- by hydrogenation o~ the a~etal-aldehyde be~ore the ~. ;
hydroly~1~-hydrogenatlon reaction.
As u~ed herein, the term polyol i~ intendod to :-~
in¢lude dlol~ a~ weli a8 tri- and higher hydro~y contalning compound~. -
.
. .
~0667Z2 C~3 / CH2 \ / C~ ~H+]
C~ -CH ~ CH-C ~ -C ~ -CHO ~ C ~ ~ H ?
.~ CH2 - 0~ OH ~~~
~ Q~ /o -'C}~
3-CH / CH-CH2-C~ -CH ~ / CH-C
The bisacet~ls tend to bc insoluble, partieularly at tempera-ture~ lo~or than th~ir ~ormation tomperature, and, as a re-sult, they precipitate out durlng operation Or the process.
Particularly in continuo w co~mercial operatlon~, the amount ~ .... ..
Or precipitat0 ~hich settles out a~ter several cycle~ can be slgni~lcant enough to cause the equipment to bocome ~: plugged, nccos~itating ~hut-do~n, clean-ou~ and a ne~
start-up. It wa8 completely unexpected, howeYer, that pre-hydrogenation o~ the cyclic acetal-aldehyde could ~olve ; this problem ~thout creating an evon greator di~iculty since it i8 ~ell kno~n that acetal gro~ps ~orm ether linkagos on hydrogenation a~ see, Por example, Re~ctions Hydrogen ~lth Or~anic Compounds over Copper, Chromium O~ido and Nlc~el Catalyst~ by Homer Adkins, P. 75. Si~ce the eth~r llnkage i8 stablo to hydrolysi~, it ~ould be ~; expected that prohydrogenatien ~ould dereat the goal Or thl~
~nvention. Contrary to this expectation it ha6 been ~ound th~t polyol8 can be easily and e~Piciently prepared w~thout the Pormation oP bisacetals and ~ithout the P~rm~tlon o~ :
ether- by hydrogenation o~ the a~etal-aldehyde be~ore the ~. ;
hydroly~1~-hydrogenatlon reaction.
As u~ed herein, the term polyol i~ intendod to :-~
in¢lude dlol~ a~ weli a8 tri- and higher hydro~y contalning compound~. -
4 _ , ,, , ," ;~
1oUi~7 Z~Z
The acetal-aldehyde~ which may be prehydrogenated and hydrolyzed and hydrogenated and, i~ desired, cyclized in accordance with thi~ invention contain one six-membered acetal ring as well as o~e aldehyde functional group attached to the acetal ring directly or, indirectly, through a cyclic or acyclic, saturated or un~aturated group which i8, in turn, attached to the acetal ring at the carbon atom which sepa-rate~ the oxygen atoms in the acetal ring.
The acetal-aldehydes to be proces~ed in accord-ance with this invention have the general formula:
R
O O
wherein X i~ -CH or -MCH in ~hich M i6 an alkyl g~oup, preferably having one to twenty carbon atoms, with the proviso that the -aH group may be attached to any M carbon atom having a replaceable hydrogen; and R~ , R4, R5 and R6 may be the same or different and may be hydrogen or an alkyl group, preferably having one to 20 carbon atom~.
Although alkyl group~ ha~ing mors than 20 carbon atoms can also be u~ed as M and Rl, R2, ~ , R49 R5 and ~6~
20 the upper limit of 20 carbon atom~ iB preferred to preclude - -too high a molecular weight. The alkyl group8 may also con-tain any ~ub~tituent~ which will not interfere with the hydrolysi~-hydrogenation reaction of the invention.
. .
Some specif~c examples o~ acetal-aldehydes which may be hydrolyzed and hydrogenated in accordance ~ith thiæ invention ~nclude ( Cl-C20) ~Q~
CH(Cl-C20)c~O
O , ~0,~
~ ~CH-CH2-C~I2-CHO
o CH a~
\C~I-CH2-CH2-CHO
., .
' 0~
(CH3)2 ~ CH-CH2-C ~ -CHO
, 0~ ~C~O ''"', ;`` ~ ~ 3 ::
.. ~ .
``.`~ o~ C~O .
3 ~ CH-CH-C~
. ' ' `~ ~ ~ CHO
~ /CH-CH-C~
O
o CHO
( CH3) 2~ ~CH-CH-CH3 J
;
~ ' , . . .
In the prehydrogenatlon reaction, any catalytic amount of any of the metal or metal compound catalysts Or the type well known and customarily re~erred to in the art as hydrogenation catalysts can be used. It i8 desirable to employ as the hydrogenation catalyst a metal or 8 compound Or a metal which may be easily and economically prepared, ~hich ha~ a high degree of activ~ty, and which retains its activity under the conditions o~ the process for a length o~ time sufricient to avoid the neces~ity Or re-activating or replacing the cataly~t at too fr~quentintervals. Generally spesking, hydrogenation catalysts uh~ch may be employed in th~ e~ecution of the process of the invention lnclude the metal hydrogenation catalysts, such as platinum, palladium, gold, silver, copper, v~nadium, ~ tungstcn, cobalt, nickel, ruthenium, rhodium, maneanese,~;
; chromium, m~lybdenum, iridium, titanium, zirconium, and the like and mixtures Or the same and compound~ and alloy~
thereof, particularly o~ides and sulrideæ thereo~, and like --hydrogenation cstalysts. Because o~ the easc and economy Nith ~hich they m~y be preparod, the base metal hydrogenation catalysts, p~rticularly the pyrophoric base metal hydrogena-tion catalysts such as nickel, cobalt, and iron, are advantageou~. Mo8t important are nickel aluminu~ alloys ~hich are activated by partial removal o~ the alumlnum ~ith NaOH. The hydrogenation ¢atalyst mu~be employed in a ~inely dividod ~orm and di~per~ed in and throughout the reaction mlxture, or it may be employed in a more ma~sive state, either in e8~entially the pure state or supported upon or carried by an inert or catalytically active ~upporting or carrier material, such a8 pumice, kieselguhr, dlatomaceous earth, clay, alumina, chaxcoal, carbon, or the like, and the reaction mixture contacted therewith a~ by , . .
.
-~lowing the mixture over or through a bed o~ the cataly8t or according to other methods that are known in the art.
me prehydrogenation ~s carried out at an elevated temperature under ~uperatmospheric hydrogen pressure. If desired, the prehydrogenation reaction can be carried out in an aqueous medium in which ca~e the uater act~ as a heat sink and a viscosity ad~ustor although the reaction can alæo be carried out neat, that is, without the use of water. If an aqueous medium i8 used, it is convenient to have enough water present ~or the hydrolysis-hydrogenation step; that i8, a molar ratio o~ -water to acetal-aldehyde o~ 100:1, pre~erably 10:1. A hydrogen pres~ure o~ 50Q - 10 000 psig, preferably 1 000 - 5 000 psig and a temperature o~ 40 -150 C. are generally used for the pxehydrogenation reaction.
The acetal-alcohol thus formed i8 then hydrolyzed and hydrogenated in an aqueou~ medium. If water i~ not -used in the prehydrogenation step, it iB now added to the ` 20 acetal-alcohol at a molar ratio of water to acetal-alcohol of 1:1 - 100:1, pre~erably 1:1 - 10:1. A hydrogen pressure ~ o~ 500 - 10 000 psig, pre~erably 1 000 - 5 000 psig and - a temperature of 65 - 150C. are employed.
The hydrogenation catalyts disclosed a~ use~ul in -the prehydrogenation step may also be used in the bYdrolysi~-hydrogenation reaction. Any strongly acidic water insoluble ion e~change resin may be used in the hydrolysis-hydrogenation reaction. Typical resin~ are tho~e containing sulfonic acid groups such as those di~closed in ~.S. Patent 2 366 007 i~ued A, 30 December 26, 1944 to G.F. D'Alelio which include sulfonated styrene-divinyl benzene copolymers commercially available as "Dowexn* MSC-l, 50 and 50 WX8; "Amberlystn* 15 and the like * denote~ trade mark resin~. Other ~ultable cation exchange resins include, for e~ample, the phenol sul~onic acid-~ormaldehyde reaction products.
The insoluble resin and the hydrogenation cataly~t Nhich form the catalyst system o~ thi~ invention may ~ist in variou~ interrelationships with one another as de~ired but typically a ~elght ratio Or insoluble resin to hydrogenation catalyst o~ 0.1:1 to 100:1, prererably 1:1 to 10:1 iB uBed.
Dependln~ on the product desired and the kind o~ reaction system employed (slurry, ~ixed b2d and 80 on), any hydrolytic-catalytic amount Or the catalyst sy~tem o~ thls invention may be employed. ~enerally, amounts o~
the acid-cataly8t ~ystem are employed such that 1% by welght o~ hydrogenation catslyst baBed on the Nelght of the scetal-alcohol i8 pre~ent. In a slurry system 1-10% by ~eight based on the content~ o~ the reactor are optimum and in a ~ixed b~d reactor, 10 to 20 times as much may be ~ u~ed.
-- 20 The reaction o~ thl~ invention may be carried ~` out ~ither continuou~ly or batchwi~. In either ca~e, the time during ~hich the reactor contents are in ¢onta¢t ~ith the cataly~t systo~ depends on the product de~ired, ` By manipulating temperature and contact time, one may produ¢e either polyol product or the cyclized rorm or ~ny polyol whi¢h i8 capablo o~ being cyclized in a ~trongly acid medlum or any combination thereo~. As temperature and contact time increa~e, the cyclization reaction i~ ;
ra~or-d. Taking BAD as an example, greater than 90% yields 30 Or cycli~ed 9AD (1~) can be obtained at higher tempera- ~ ;
ture~ and contact times while 99% yield~ Or BAD c~n be 9 ~ :-~ 6 ~Z ~
obtained at lower temperatures and contact times. Any interrelationship between temperature and contact time o~
up to 3 hours at 60C. and up to one hal~ hour at 150C.
can be ob~erved. At 130C. or higher, THF ~orm~ very rapidly and pre~erentially. Other methods ~or producing 1~ uslng cation exchange resins are disclo~ed in U.S.
Patent 3,467,679 i~ued September 16, 1969 to A.O. Rogers and aerman Patent 850,750 issued September 29, 1952 to I.a. Faxbenindustrie.
The polyols produced by the process o~ this in~ention may be used ~or any application Por which polyol~
are suitable such as reactant~ ~ith isocyanates to form urethanes and polyurethanes, with acids to form esters and polyesters and 80 on.
The invention is further illustrated but i~ not intended to be limited by the ~ollowing examples in which all parts and percentage~ are by weight unless otherwi~e speci~ied.
,.... EXA~E 1 '~
A 40 g. mi~ture o~ the monocyclic acetals, 2-(3~
propanal)-5,5-dimethyl-1,3-dioxane (90 and 2-(2~-propanal)-
1oUi~7 Z~Z
The acetal-aldehyde~ which may be prehydrogenated and hydrolyzed and hydrogenated and, i~ desired, cyclized in accordance with thi~ invention contain one six-membered acetal ring as well as o~e aldehyde functional group attached to the acetal ring directly or, indirectly, through a cyclic or acyclic, saturated or un~aturated group which i8, in turn, attached to the acetal ring at the carbon atom which sepa-rate~ the oxygen atoms in the acetal ring.
The acetal-aldehydes to be proces~ed in accord-ance with this invention have the general formula:
R
O O
wherein X i~ -CH or -MCH in ~hich M i6 an alkyl g~oup, preferably having one to twenty carbon atoms, with the proviso that the -aH group may be attached to any M carbon atom having a replaceable hydrogen; and R~ , R4, R5 and R6 may be the same or different and may be hydrogen or an alkyl group, preferably having one to 20 carbon atom~.
Although alkyl group~ ha~ing mors than 20 carbon atoms can also be u~ed as M and Rl, R2, ~ , R49 R5 and ~6~
20 the upper limit of 20 carbon atom~ iB preferred to preclude - -too high a molecular weight. The alkyl group8 may also con-tain any ~ub~tituent~ which will not interfere with the hydrolysi~-hydrogenation reaction of the invention.
. .
Some specif~c examples o~ acetal-aldehydes which may be hydrolyzed and hydrogenated in accordance ~ith thiæ invention ~nclude ( Cl-C20) ~Q~
CH(Cl-C20)c~O
O , ~0,~
~ ~CH-CH2-C~I2-CHO
o CH a~
\C~I-CH2-CH2-CHO
., .
' 0~
(CH3)2 ~ CH-CH2-C ~ -CHO
, 0~ ~C~O ''"', ;`` ~ ~ 3 ::
.. ~ .
``.`~ o~ C~O .
3 ~ CH-CH-C~
. ' ' `~ ~ ~ CHO
~ /CH-CH-C~
O
o CHO
( CH3) 2~ ~CH-CH-CH3 J
;
~ ' , . . .
In the prehydrogenatlon reaction, any catalytic amount of any of the metal or metal compound catalysts Or the type well known and customarily re~erred to in the art as hydrogenation catalysts can be used. It i8 desirable to employ as the hydrogenation catalyst a metal or 8 compound Or a metal which may be easily and economically prepared, ~hich ha~ a high degree of activ~ty, and which retains its activity under the conditions o~ the process for a length o~ time sufricient to avoid the neces~ity Or re-activating or replacing the cataly~t at too fr~quentintervals. Generally spesking, hydrogenation catalysts uh~ch may be employed in th~ e~ecution of the process of the invention lnclude the metal hydrogenation catalysts, such as platinum, palladium, gold, silver, copper, v~nadium, ~ tungstcn, cobalt, nickel, ruthenium, rhodium, maneanese,~;
; chromium, m~lybdenum, iridium, titanium, zirconium, and the like and mixtures Or the same and compound~ and alloy~
thereof, particularly o~ides and sulrideæ thereo~, and like --hydrogenation cstalysts. Because o~ the easc and economy Nith ~hich they m~y be preparod, the base metal hydrogenation catalysts, p~rticularly the pyrophoric base metal hydrogena-tion catalysts such as nickel, cobalt, and iron, are advantageou~. Mo8t important are nickel aluminu~ alloys ~hich are activated by partial removal o~ the alumlnum ~ith NaOH. The hydrogenation ¢atalyst mu~be employed in a ~inely dividod ~orm and di~per~ed in and throughout the reaction mlxture, or it may be employed in a more ma~sive state, either in e8~entially the pure state or supported upon or carried by an inert or catalytically active ~upporting or carrier material, such a8 pumice, kieselguhr, dlatomaceous earth, clay, alumina, chaxcoal, carbon, or the like, and the reaction mixture contacted therewith a~ by , . .
.
-~lowing the mixture over or through a bed o~ the cataly8t or according to other methods that are known in the art.
me prehydrogenation ~s carried out at an elevated temperature under ~uperatmospheric hydrogen pressure. If desired, the prehydrogenation reaction can be carried out in an aqueous medium in which ca~e the uater act~ as a heat sink and a viscosity ad~ustor although the reaction can alæo be carried out neat, that is, without the use of water. If an aqueous medium i8 used, it is convenient to have enough water present ~or the hydrolysis-hydrogenation step; that i8, a molar ratio o~ -water to acetal-aldehyde o~ 100:1, pre~erably 10:1. A hydrogen pres~ure o~ 50Q - 10 000 psig, preferably 1 000 - 5 000 psig and a temperature o~ 40 -150 C. are generally used for the pxehydrogenation reaction.
The acetal-alcohol thus formed i8 then hydrolyzed and hydrogenated in an aqueou~ medium. If water i~ not -used in the prehydrogenation step, it iB now added to the ` 20 acetal-alcohol at a molar ratio of water to acetal-alcohol of 1:1 - 100:1, pre~erably 1:1 - 10:1. A hydrogen pressure ~ o~ 500 - 10 000 psig, pre~erably 1 000 - 5 000 psig and - a temperature of 65 - 150C. are employed.
The hydrogenation catalyts disclosed a~ use~ul in -the prehydrogenation step may also be used in the bYdrolysi~-hydrogenation reaction. Any strongly acidic water insoluble ion e~change resin may be used in the hydrolysis-hydrogenation reaction. Typical resin~ are tho~e containing sulfonic acid groups such as those di~closed in ~.S. Patent 2 366 007 i~ued A, 30 December 26, 1944 to G.F. D'Alelio which include sulfonated styrene-divinyl benzene copolymers commercially available as "Dowexn* MSC-l, 50 and 50 WX8; "Amberlystn* 15 and the like * denote~ trade mark resin~. Other ~ultable cation exchange resins include, for e~ample, the phenol sul~onic acid-~ormaldehyde reaction products.
The insoluble resin and the hydrogenation cataly~t Nhich form the catalyst system o~ thi~ invention may ~ist in variou~ interrelationships with one another as de~ired but typically a ~elght ratio Or insoluble resin to hydrogenation catalyst o~ 0.1:1 to 100:1, prererably 1:1 to 10:1 iB uBed.
Dependln~ on the product desired and the kind o~ reaction system employed (slurry, ~ixed b2d and 80 on), any hydrolytic-catalytic amount Or the catalyst sy~tem o~ thls invention may be employed. ~enerally, amounts o~
the acid-cataly8t ~ystem are employed such that 1% by welght o~ hydrogenation catslyst baBed on the Nelght of the scetal-alcohol i8 pre~ent. In a slurry system 1-10% by ~eight based on the content~ o~ the reactor are optimum and in a ~ixed b~d reactor, 10 to 20 times as much may be ~ u~ed.
-- 20 The reaction o~ thl~ invention may be carried ~` out ~ither continuou~ly or batchwi~. In either ca~e, the time during ~hich the reactor contents are in ¢onta¢t ~ith the cataly~t systo~ depends on the product de~ired, ` By manipulating temperature and contact time, one may produ¢e either polyol product or the cyclized rorm or ~ny polyol whi¢h i8 capablo o~ being cyclized in a ~trongly acid medlum or any combination thereo~. As temperature and contact time increa~e, the cyclization reaction i~ ;
ra~or-d. Taking BAD as an example, greater than 90% yields 30 Or cycli~ed 9AD (1~) can be obtained at higher tempera- ~ ;
ture~ and contact times while 99% yield~ Or BAD c~n be 9 ~ :-~ 6 ~Z ~
obtained at lower temperatures and contact times. Any interrelationship between temperature and contact time o~
up to 3 hours at 60C. and up to one hal~ hour at 150C.
can be ob~erved. At 130C. or higher, THF ~orm~ very rapidly and pre~erentially. Other methods ~or producing 1~ uslng cation exchange resins are disclo~ed in U.S.
Patent 3,467,679 i~ued September 16, 1969 to A.O. Rogers and aerman Patent 850,750 issued September 29, 1952 to I.a. Faxbenindustrie.
The polyols produced by the process o~ this in~ention may be used ~or any application Por which polyol~
are suitable such as reactant~ ~ith isocyanates to form urethanes and polyurethanes, with acids to form esters and polyesters and 80 on.
The invention is further illustrated but i~ not intended to be limited by the ~ollowing examples in which all parts and percentage~ are by weight unless otherwi~e speci~ied.
,.... EXA~E 1 '~
A 40 g. mi~ture o~ the monocyclic acetals, 2-(3~
propanal)-5,5-dimethyl-1,3-dioxane (90 and 2-(2~-propanal)-
5,5-dimethy1-1,3-dloxane (100 is hydrogenated at 60C., `;~ using 5 g. of Raney nickel and 2500 p8ig of hydrogen. The ., reaction time i~ 50 minutes and the reactant ald~hydes are completely converted to their cQrresponding alcohols, i.e., , the monocyclic acetal~ 2-(3'-propanol)-5,5-dimethyl-1,3-dioxane and 2-(2~-propanol)-5,5-dimethyl-1,3-dioxane.
. j ~.
., .
. .~
- , . .: . . . - , - ~
H~drolysis/kydrogenation The mixture o~ the cyclic acetals prepared above is reacted with 20 g. o~ water in the presence of five grams o~ 30 mesh cross-linked sulfonated polystyrene ("Dowex" -50) and 5 g. of Raney nickel at 85C.. and hydro-gena~ed with 1 000 psig o~ hydrogen for one hour. Gas chromatographic analysls indicates that the linear isomer undergoes 86% conversion to yield 0.4 mole percent tetra-hydro~uran and 99.6 mole percent 1,4-butanedlol. me branched isomer undergoes only 42% conver~ion.
In an identical reaction except that the tempera-ture is 130C., the linear isomer undergoe~ 99.2% conver-sion and yields 52 mole percent tetrahydrofuran and 48 mole percent 1,4-butanediol.
The prehydrogenation and hydrolysis-hydrogenation procedure de~cribed in Example 1 is repeated except that a 40 gram mixture o~ the acetal-aldehydes describèd in the following table are used.
`~ ' ... .' ... . .
. ~
.,~
.
r`
~,: ', ' ' ~1 .
.`' ',; '' -11- .
'i . - : :' ., ~ ~ - .
~06~;7ZZ
~o ~ , ~
.~ ~ ~: o~
' m ~ a~ .
~ ~1 ~D 0. U~
E~ O ~ o o I
g U~
`-1 H
CO ~D 1`
P ~ co a~
o -, C~
. . , , ` .
t~ U
U~ o U) . E~ oo o~ co ", .. ~
~ I .
. Cq ~ ~ ~ ~
.; ~ I .,, .,1 ~ ,.
_l '' aJ ~ ~ ~ U~ o ,~ ~ ~
~:` ~ :C
.~ .
.~ O
E~ o ~
, E~
; a~ I
.~ d ~
,~` E~
O o o o .,~ ~ U~
.. ~ .
. ` ` .
l x l x l x ~ x ~ l ' _ O ~ O ~ O ~ O
~; d ~a -d ~ d 'd ` 'a d ` d `
~, d ') ~J ~ ~ ~ ~ r~ ~ I ~D d ~ 'r .~ D. ~ Q, ~ ~ ` Q. ` Q
0-~1 0 ~1 0 ~1 0 ~ O :~. O :~
'O ~ I ~ Ih I 1~l 1 ~ S ID 5~ S IU
: ~ ' .C ' .~ X ' ~ x .i . OQ ~ ~ tP ~ ~ t~ JJ "p ~ ~ ~p ~." o ~ o U ~ ~ ~I N ~ N ~
,t ~ ~ :
W
.
106~;7ZZ
A hundred grams of 2-(3t-propanal)-5,5-dimethyl-1,3-dioxane 84~ and 2-(2'-propanal)-5,5-dimethyl-1,3-dioxane 16% are treated with hydrogen at 1 000 p8ig hydrogen presæure in the presence of 5 g. of Raney nickel at 80C. The reaction i8 co~plete in 60 minute~. The reaction product i8 then ~iltered and reacted with 50 gram~
Or water and hydrogen at 1 000 psig hydrogen pres~ure in the presence of 5 grams o~ a cross-linked sul~onated poly-styrene ("Dowex" 50) and 5 grams o~ Raney nickel, for 2hour~ at 80C. An 80% conversion is obtained and the yield contains 0.9 mole percent tetrahydr~uran and 98 ; mole percent of 1,4-butanediol.
It is to be understood that any Or the compo-nents and conditions mentioned as suitable herein can be substituted for its counterpart in the ~oregoing examples and that although the invention has been described ln considerable detail in the ~oregoing, such detail is solely for the purpose of illustration. Variations can 20 be made in the invention by those skilled in the art ~`
without departing from the spirit and scope of the inven-tion except a~ set forth in the claims.
` ~'.'~
. . .
~; , "~' .
'~?, . . ~
', ,.: ., ' ' .,
. j ~.
., .
. .~
- , . .: . . . - , - ~
H~drolysis/kydrogenation The mixture o~ the cyclic acetals prepared above is reacted with 20 g. o~ water in the presence of five grams o~ 30 mesh cross-linked sulfonated polystyrene ("Dowex" -50) and 5 g. of Raney nickel at 85C.. and hydro-gena~ed with 1 000 psig o~ hydrogen for one hour. Gas chromatographic analysls indicates that the linear isomer undergoes 86% conversion to yield 0.4 mole percent tetra-hydro~uran and 99.6 mole percent 1,4-butanedlol. me branched isomer undergoes only 42% conver~ion.
In an identical reaction except that the tempera-ture is 130C., the linear isomer undergoe~ 99.2% conver-sion and yields 52 mole percent tetrahydrofuran and 48 mole percent 1,4-butanediol.
The prehydrogenation and hydrolysis-hydrogenation procedure de~cribed in Example 1 is repeated except that a 40 gram mixture o~ the acetal-aldehydes describèd in the following table are used.
`~ ' ... .' ... . .
. ~
.,~
.
r`
~,: ', ' ' ~1 .
.`' ',; '' -11- .
'i . - : :' ., ~ ~ - .
~06~;7ZZ
~o ~ , ~
.~ ~ ~: o~
' m ~ a~ .
~ ~1 ~D 0. U~
E~ O ~ o o I
g U~
`-1 H
CO ~D 1`
P ~ co a~
o -, C~
. . , , ` .
t~ U
U~ o U) . E~ oo o~ co ", .. ~
~ I .
. Cq ~ ~ ~ ~
.; ~ I .,, .,1 ~ ,.
_l '' aJ ~ ~ ~ U~ o ,~ ~ ~
~:` ~ :C
.~ .
.~ O
E~ o ~
, E~
; a~ I
.~ d ~
,~` E~
O o o o .,~ ~ U~
.. ~ .
. ` ` .
l x l x l x ~ x ~ l ' _ O ~ O ~ O ~ O
~; d ~a -d ~ d 'd ` 'a d ` d `
~, d ') ~J ~ ~ ~ ~ r~ ~ I ~D d ~ 'r .~ D. ~ Q, ~ ~ ` Q. ` Q
0-~1 0 ~1 0 ~1 0 ~ O :~. O :~
'O ~ I ~ Ih I 1~l 1 ~ S ID 5~ S IU
: ~ ' .C ' .~ X ' ~ x .i . OQ ~ ~ tP ~ ~ t~ JJ "p ~ ~ ~p ~." o ~ o U ~ ~ ~I N ~ N ~
,t ~ ~ :
W
.
106~;7ZZ
A hundred grams of 2-(3t-propanal)-5,5-dimethyl-1,3-dioxane 84~ and 2-(2'-propanal)-5,5-dimethyl-1,3-dioxane 16% are treated with hydrogen at 1 000 p8ig hydrogen presæure in the presence of 5 g. of Raney nickel at 80C. The reaction i8 co~plete in 60 minute~. The reaction product i8 then ~iltered and reacted with 50 gram~
Or water and hydrogen at 1 000 psig hydrogen pres~ure in the presence of 5 grams o~ a cross-linked sul~onated poly-styrene ("Dowex" 50) and 5 grams o~ Raney nickel, for 2hour~ at 80C. An 80% conversion is obtained and the yield contains 0.9 mole percent tetrahydr~uran and 98 ; mole percent of 1,4-butanediol.
It is to be understood that any Or the compo-nents and conditions mentioned as suitable herein can be substituted for its counterpart in the ~oregoing examples and that although the invention has been described ln considerable detail in the ~oregoing, such detail is solely for the purpose of illustration. Variations can 20 be made in the invention by those skilled in the art ~`
without departing from the spirit and scope of the inven-tion except a~ set forth in the claims.
` ~'.'~
. . .
~; , "~' .
'~?, . . ~
', ,.: ., ' ' .,
Claims (6)
1. In a process for the hydrolysis and hydrogenation of a cyclic acetal, having a formula of wherein X is or in which M is alkyl and R1, R2, R3, R4, R5 and R6 are the same or different hydrogen or alkyl group and wherein the alkyl groups of M, R1, R2 R3, R4, R5 and R6 contain one to 20 carbon atoms, by contacting the cyclic acetal in an aqueous medium with hydrogen and a strongly acidic water insoluble ion ex-change resin and a hydrogenation catalyst, at a molar ratio of water to cyclic acetal of 1:1 to 100:1, the improvement which comprises prehydrogenating the cyclic acetal, at a temperature between 40° and 150°C, in the presence of hydrogen and a catalytic amount of a Raney nickel catalyst.
2. The improvement of Claim 1 wherein the prehydrogenation is carried out in an aqueous medium.
3. The improvement of Claim 1 wherein the hydrogen is present during the prehydrogenation at a pressure of 500 - 10 000 psig.
4. The improvement of Claim 1 wherein the prehydrogenation is carried out neat.
5. The improvement of Claim 1 wherein the cyclic acetal-aldehyde is 2(2'-propanal)-5methyl dioxane.
6. The improvement of Claim 1 wherein the cyclic acetal-aldehyde is 2(3'-propanal)-5-methyl dioxane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49429174A | 1974-08-02 | 1974-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066722A true CA1066722A (en) | 1979-11-20 |
Family
ID=23963875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,645A Expired CA1066722A (en) | 1974-08-02 | 1975-07-31 | Two-step method for hydrolyzing and hydrogenating acetal-aldehydes |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5139615A (en) |
| CA (1) | CA1066722A (en) |
| DE (1) | DE2524039A1 (en) |
| GB (1) | GB1486379A (en) |
| IT (1) | IT1040456B (en) |
| NL (1) | NL7509206A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096192A (en) * | 1976-03-30 | 1978-06-20 | E. I. Du Pont De Nemours And Company | Process for the preparation of 2-methyl-1,3-propanediol |
| GB1581379A (en) * | 1976-12-28 | 1980-12-10 | Du Pont | Preparation of diols by hydrogenation and hyrdrolysis of cyclic acetals |
| JPS5581058A (en) * | 1978-12-13 | 1980-06-18 | Ube Ind Ltd | Injection method and device of die-casting machine |
| BR8004345A (en) * | 1979-09-25 | 1981-04-28 | Nl Industries Inc | WEAR MALE TO BE USED IN A PRESSURE CASTING TEMPLATE AND PROCESS FOR FORMING, FROM CAST METAL, A PRESSURE CASTING PIECE WITH A UNDERGROUND REGION |
| US5166370A (en) * | 1991-04-12 | 1992-11-24 | Arco Chemical Technology, L.P. | Preparation of tetrahydrofuran using a supported transition metal |
| JPH06254657A (en) * | 1993-03-04 | 1994-09-13 | Hanano Shoji Kk | Treatment of forming surface in mold for shell molding |
-
1975
- 1975-05-30 DE DE19752524039 patent/DE2524039A1/en not_active Withdrawn
- 1975-07-31 CA CA232,645A patent/CA1066722A/en not_active Expired
- 1975-07-31 GB GB3212275A patent/GB1486379A/en not_active Expired
- 1975-08-01 IT IT2604375A patent/IT1040456B/en active
- 1975-08-01 JP JP9327575A patent/JPS5139615A/en active Pending
- 1975-08-01 NL NL7509206A patent/NL7509206A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2524039A1 (en) | 1976-02-19 |
| NL7509206A (en) | 1976-02-04 |
| JPS5139615A (en) | 1976-04-02 |
| IT1040456B (en) | 1979-12-20 |
| GB1486379A (en) | 1977-09-21 |
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