Hydroformylation process for producing 1,6-disubstituted hexane derivatives

Patent metadata

Field	Value
Publication number	US-10647651-B2
Application number	US-201615767393-A
Country	US
Kind code	B2
Filing date	Oct 11, 2016
Priority date	Oct 12, 2015
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The invention relates to a process for the production of 1,6-difunctionalized hexane derivatives from 1,3-diunsaturated hydrocarbons, preferably butadiene, wherein a hydroformylation with carbon monoxide and hydrogen is performed in the presence of an at least dihydric alkanol and during the hydroformylation the temperature is increased. The reaction yields the acetals of the 1,6-hexanedial derivatives which are isolated and further reacted to obtain the desired 1,6-difunctionalized hexane derivatives, in particular 1,6-hexanediamine, 1,6-hexanediol and adipic acid.

First claim

The invention claimed is:

1. A process for the production of a compound of the formula (I)

wherein
X are both CH 2 NH 2 , CH 2 OH or COOH,
R 1 and R 2 are independently from each other hydrogen or linear or branched C 1 -C 4 -alkyl,
comprising the following steps:
i) subjecting at least one compound of the formula (II)

wherein R 1 and R 2 have the same meaning as in formula (I),
to a hydroformylation with carbon monoxide and hydrogen in the presence of at least one transition metal catalyst,
wherein the hydroformylation is performed in the presence of at least one alkanol of the formula (III)
HO—Z—OH  (III)

wherein
Z is a hydrocarbon chain having 2 or 3 carbon atoms which is unsubstituted or substituted and which may be part of a carbocycle, a heterocycle or an aromatic or heteroaromatic ring,
wherein during the hydroformylation the temperature is increased for at least 10° C. from a temperature T 1 to a temperature T 2 ,
to obtain a reaction mixture comprising at least one compound selected from the compounds of the formula (IV.a) and (IV.b),

wherein
Z has the same meaning as in formula (III), and
R 1 and R 2 have the same meaning as in formula (I),

ii) subjecting the reaction mixture obtained in step i) to a separation to obtain a fraction enriched with at least one compound selected from the compounds of the formula (IV.a) and (IV.b) and a fraction depleted with at least one compound selected from the compounds of the formula (IV.a) and (IV.b),
iii) optionally recycling at least partially the fraction depleted with at least one compound selected from the compounds of the formula (IV.a) and (IV.b) obtained in step ii) to step i), and
iv) subjecting the fraction enriched with at least one compound selected from the compounds of the formula (IV.a) and (IV.b) obtained in step ii) to a reaction in which the acetal groups in the compounds of the formula (IV.a) and (IV.b) are reacted to obtain the compound of the formula (I).

2. The process according to claim 1 , wherein the at least one compound of the formula (II) is butadiene.

3. The process according to claim 1 , wherein the temperature is increased from T 1 to T 2 after at least 50 mol-% of the double bond equivalents of the at least one compound of the formula (II) are reacted.

4. The process according to claim 1 , wherein T 1 is at least 40° C.

5. The process according to claim 1 , wherein T 2 is at least 110° C.

6. The process according to claim 1 , wherein T 1 is in the range from 40 to 100° C. and T 2 is in the range from 110 to 150° C.

7. The process according to claim 1 , wherein in step i) the pressure is decreased.

8. The process according to claim 1 , wherein the molar ratio of the at least one compound of the formula (II) to the at least one alkanol of the formula (III) is in the range from 1:1 to 1:100.

9. The process according to claim 1 , wherein step i) is performed in the presence of at least one acid.

10. The process according to claim 1 , wherein the at least one transition metal catalyst comprises at least one transition metal selected from Co, Ru, Ir, Rh, Ni, Pd and Pt.

11. The process according to claim 9 , wherein the at least one transition metal catalyst comprises at least one bidentate ligand which is bound over two P atoms to a transition metal and wherein the bidentate ligand has a natural bite-angle in the range from 90° to 1300.

12. The process according to claim 1 , wherein the at least one transition metal catalyst comprises at least one ligand of the formula (V)

wherein
R A , R B , R C and R D are independently from each other alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals may carry 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, carboxyl, SO 3 H, sulfonate, NE 1 E 2 , NE 1 E 2 E 3+ X − , halogen, nitro, formyl, acyl and cyano, wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen, alkyl, cycloalkyl, and aryl and X − is an anion equivalent,
and wherein the radicals cycloalkyl, heterocycloalkyl, aryl and hetaryl R A , R B , R C and R D may carry 1, 2, 3, 4 or 5 substituents selected from alkyl and the substituents mentioned for the alkyl radicals R A , R B , R C and R D before, or

R A and R B and/or R C and R D together with the P atom and, if present, the groups X 1 , X 2 , X 5 and X 6 to which they are bound, are a 5- to 8-membered heterocycle which is optionally fused with one, two or three groups selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl, wherein the heterocycle and, if present, the fused-on groups independently from each other may each carry 1, 2, 3 or 4 substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, carboxyl, SO 3 H, sulfonate, NE 4 E 5 , NE 4 E 5 E 6+ X − , nitro, alkoxycarbonyl, formyl, acyl and cyano, wherein E 4 , E 5 and E 6 are the same or different and are selected from hydrogen, alkyl, cycloalkyl and aryl and X − is an anion equivalent,
X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently from each other O, S, SiR x R y or NR z , wherein R x , R y and R z are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
Y is a divalent bridging group which contains carbon atoms, and
a, b, c, d, e and f are independently from each other 0 or 1.

13. The process according to claim 1 , wherein the at least one transition metal catalyst comprises at least one ligand of the formula (V.1)

Wherein
Y is a divalent bridging group which contains carbon atoms,
c and d are independently from each other 0 or 1, and
the radicals R A* , R B* , R C* and R D* are independently from each other selected from the groups of the formula (VI.a) to (VI.k)

wherein
Alk is a C 1 -C 4 -alkyl group, and
R a , R b , R c and R d are independently from each other hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, formyl, acyl, halogen, C 1 -C 4 -alkoxycarbonyl or carboxyl.

14. The process according to claim 1 , wherein the at least one transition metal catalyst comprises at least one ligand of the formula (VII)

wherein
Y is a divalent bridging group which contains carbon atoms,
Q 1 and Q 2 are independently from each other a divalent bridging group of the formula (VIII),

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Paciello Rocco
• Ernst Martin
• Mormul Jaroslaw
• Hofmann Peter
• Breitenfeld Jan
• Trapp Oliver

Classifications

• C07C51/305

  with sulfur or sulfur-containing compounds · CPC title

• C07C31/20

  Dihydroxylic alcohols · CPC title

• C07C29/74

  Separation; Purification; Use of additives, e.g. for stabilisation · CPC title

• C07C209/26 Primary

  by reduction with hydrogen · CPC title

• C08G69/28

  Preparatory processes · CPC title