US4017550A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Manufacture of 1,4-butanediol
Assignee: BASF SE
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Filing: 1974-12-30
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Granted: 1977-04-12
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Expires: 1994-12-30
Abstract
Abstract The manufacture of 1,4-butanediol by hydroformylation of cyclic acetals of acrolein in the presence of phosphine-modified cobalt carbonyl complexes or rhodium carbonyl complexes and hydrogenation of the 3-formylpropionaldehyde-acetals which are the principal products first formed.
Inventors
- 👤 Rudolf Kummer
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:06
CPC Classifications
C; C07; C07C; C07C29/00; C07C29/132; C07C29/136; C07C29/14; C07C29/141
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
94 words
A process for the manufacture of 1,4-butanediol, wherein cyclic acetals of acrolein are reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl complexes or rhodium carbonyl complexes which are modified with tertiary organic phosphines, at temperatures of from 80° to 200° C under superatmospheric pressure, and the resulting 3-formylpropionaldehyde-acetals and the 4-hydroxybutyraldehyde-acetals produced are hydrogenated in the presence of water at 70°-150° C and under superatmospheric pressure in the presence of a hydrogenation catalyst containing a metal of group 8 of the Periodic Table or copper as a catalytically active metal.
Claim 2
Dependent Claim
94 words
A process for the manufacture of 1,4-butanediol, wherein cyclic acetals of acrolein are reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl complexes or rhodium carbonyl complexes which are modified with tertiary organic phosphines, at temperatures of from 80° to 200° C under superatmospheric pressure, and the resulting 3-formylpropionaldehyde-acetals and the 4-hydroxybutyraldehyde-acetals produced are hydrogenated in the presence of water at 70°-150° C and under superatmospheric pressure in the presence of a hydrogenation catalyst containing a metal of group 8 of the Periodic Table or copper as a catalytically active metal.
Claim 3
Dependent Claim
20 words
A process as claimed in claim 1, wherein the acetal of acrolein with 2-methyl-1,3-propanediol is used as the starting material.
Claim 4
Dependent Claim
25 words
A process as claimed in claim 1, wherein tri-C 1 - to C 20 -alkylphosphines or triphenylphosphine are used as modifiers in the hydroformylation reaction.
Claim 5
Dependent Claim
30 words
A process as claimed in claim 1, wherein, in the case of rhodium catalysts, from 5 to 50 moles of tertiary organic phosphines are employed per gram atom of rhodium.
Claim 6
Dependent Claim
30 words
A process as claimed in claim 1, wherein, in the case of cobalt catalysts, from 1 to 20 moles of tertiary organic phosphines are employed per gram atom of cobalt.
Claim 7
Dependent Claim
29 words
A process as claimed in claim 1, wherein from 1 to 30 moles of water are employed in the hydrogenation reaction, per mole of the hydroformylation products first obtained.
Claim 8
Dependent Claim
41 words
A process as claimed in claim 1 wherein said tertiary organic phosphine is a tri-C 1 to C 30 -alkyl phosphine, a triarylphosphine, a tertiary alkylphenyl phosphine, or one of said phosphines having one or more methoxy, carbonyl or carbalkoxy groups.
Claim 9
Dependent Claim
20 words
A process as claimed in claim 1 wherein said tertiary organic phosphine is a tri-C 1 to C 30 -trialkylphosphine.
Claim 10
Dependent Claim
16 words
A process as claimed in claim 1 wherein said tertiary organic phosphine is triphenylphosphine or tritolylphosphine.
Claim 11
Dependent Claim
19 words
A process as claimed in claim 1 wherein said hydrogenation catalyst is a nickel, cobalt or copper hydrogenation catalyst.
Claim 12
Dependent Claim
18 words
A process as claimed in claim 1 wherein said catalyst contains, as an activator, copper, zinc or chromium.
Claim 13
Dependent Claim
17 words
A process as claimed in claim 1 wherein said hydrogenation catalyst is Raney nickel or Raney cobalt.
Claim 14
Dependent Claim
18 words
A process as claimed in claim 1 wherein said hydrogenation catalyst is an adkins copper/chromium oxide hydrogenation catalyst.
Claim 15
Dependent Claim
91 words
A process for preparing 1,4-butanediol which comprises hydroformylating a cyclic acetal of acrolein and an alkanediol of up to 4 carbon atoms in the presence of a cobalt carbonyl complex or a rhodium carbonyl complex, said complexes being modified by a tertiary organic phosphine, at temperatures of from 80° to 200° C under superatmospheric pressure to produce the corresponding cyclic acetals of formylpropionaldehydes, and hydrogenating the corresponding cyclic acetals of formylpropionaldehydes at elevated temperatures and under superatmospheric pressure in the presence of a hydrogenation catalyst and in the presence of water.
Claim 16
Dependent Claim
91 words
A process for preparing 1,4-butanediol which comprises hydroformylating a cyclic acetal of acrolein and an alkanediol of up to 4 carbon atoms in the presence of a cobalt carbonyl complex or a rhodium carbonyl complex, said complexes being modified by a tertiary organic phosphine, at temperatures of from 80° to 200° C under superatmospheric pressure to produce the corresponding cyclic acetals of formylpropionaldehydes, and hydrogenating the corresponding cyclic acetals of formylpropionaldehydes at elevated temperatures and under superatmospheric pressure in the presence of a hydrogenation catalyst and in the presence of water.
Claim 17
Dependent Claim
22 words
A process as claimed in claim 14 wherein said cyclic acetal is the cyclic acetal of acrolein and 1,3-propanediol, 1,3-butanediol, or 2-methyl-1,3-propanediol.
Claim 18
Dependent Claim
48 words
A process as claimed in claim 14 wherein the hydrogenation is carried out at 70-150° C and at superatmospheric pressure in the presence of a catalytic amount of a hydrogenation catalyst containing a metal of group 8 of the Periodic Table or copper as a catalytically active metal.
Claim 19
Dependent Claim
85 words
A process for preparing 1,4-butanediol which comprises hydroformylating a cyclic acetal of acrolein and 2-methyl-1,3-propanediol in the presence of a cobalt carbonyl complex or a rhodium carbonyl complex, said complexes being modified by a tertiary organic phosphine, at temperatures of from 80° to 200° C and superatmospheric pressure to produce formylpropionaldehyde acetals of 2-methyl-1,3-propanediol, and hydrogenating the resulting acetals at elevated temperatures and pressure in the presence of water and in the presence of a hydrogenation catalyst to produce a mixture of 1,4-butanediol and 2-methyl-1,3-propanediol.
Claim 20
Dependent Claim
85 words
A process for preparing 1,4-butanediol which comprises hydroformylating a cyclic acetal of acrolein and 2-methyl-1,3-propanediol in the presence of a cobalt carbonyl complex or a rhodium carbonyl complex, said complexes being modified by a tertiary organic phosphine, at temperatures of from 80° to 200° C and superatmospheric pressure to produce formylpropionaldehyde acetals of 2-methyl-1,3-propanediol, and hydrogenating the resulting acetals at elevated temperatures and pressure in the presence of water and in the presence of a hydrogenation catalyst to produce a mixture of 1,4-butanediol and 2-methyl-1,3-propanediol.
Claim 21
Dependent Claim
49 words
A process as claimed in claim 17 wherein said formylpropionaldehyde acetals of 2-methyl-1,3-propanediol are hydrogenated in the presence of from at least the stoichiometric amount up to a 30-fold molar excess of water at a temperature of 70° - 150° C. and a pressure of 100 - 300 atmospheres.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-04-11 | 1980-10-11 | 1981-04-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-04-11 | 1984-10-11 | 1985-04-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-04-11 | 1988-10-11 | 1989-04-12 | $7700.00 | Window Closed / Lapsed |