Search

CN-116568662-B - Production of 2, 4-tetramethyl cyclobutane-1, 3-diol from secondary alcohol and 2, 4-tetramethyl cyclobutanedione using homogeneous catalyst

CN116568662BCN 116568662 BCN116568662 BCN 116568662BCN-116568662-B

Abstract

The present invention discloses a process for the preparation of 2, 4-tetramethylcyclobutane-1, 3-diol by reacting 2, 4-tetramethylcyclobutane dione with a secondary alcohol in the presence of a transfer hydrogenation catalyst.

Inventors

  • M.E. Yangka
  • R. T. Humber
  • S. D. Bannik
  • KLINE ROBERT STERLING
  • S. R. Taistman

Assignees

  • 伊士曼化工公司

Dates

Publication Date
20260512
Application Date
20211130
Priority Date
20201204

Claims (20)

  1. 1. A process for producing 2, 4-tetramethylcyclobutane-1, 3-diol comprising: (i) Contacting 2, 4-tetramethylcyclobutanedione with a secondary alcohol in the presence of a transfer hydrogenation catalyst to produce 3-hydroxy-2, 4-tetramethylcyclobutanone and the corresponding ketone derived from the secondary alcohol, and (Ii) Contacting 3-hydroxy-2, 4-tetramethyl cyclobutanone with a secondary alcohol in the presence of a transfer hydrogenation catalyst to produce 2, 4-tetramethyl cyclobutane-1, 3-diol and a corresponding ketone derived from the secondary alcohol, wherein the ketone is optionally removed by reactive distillation; Wherein the transfer hydrogenation catalyst is one or more of H 2 Ru(PPh 3 ) 4 、Ru 3 (CO) 12 、(Ar 4 C 4 CO)Ru(CO) 3 and (Ar 4 C 4 CO) 2 H(μ-H)(CO) 4 Ru 2 ), and Wherein (Ar 4 C 4 CO)Ru(CO) 3 is represented by the following formula: and Ar is represented by the following general formula: And the radicals R are identical or different and are selected from H, methyl, ethyl, or straight-chain or branched alkyl having 3 to 10 carbon atoms, substituted or unsubstituted aryl, carbonyl-containing radicals, amino having 2 to 12 carbon atoms, alkoxy having 3 to 10 carbon atoms, nitrile, fluorine or fluorinated hydrocarbon radicals; and wherein (Ar 4 C 4 CO) 2 H(μ-H)(CO) 4 Ru 2 is represented by the following general formula: and Ar is represented by the following general formula: And the radicals R are identical or different and are selected from H, methyl, ethyl, or straight-chain or branched alkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted aryl radicals, carbonyl-containing radicals, amino radicals having 2 to 12 carbon atoms, alkoxy radicals having 3 to 10 carbon atoms, nitrile, fluorine or fluorinated hydrocarbon radicals.
  2. 2. The process according to claim 1, wherein the radicals R, identical or different, are chosen from ester or amide groups having from 2 to 12 carbon atoms, perfluorobutyl or pentafluorophenyl.
  3. 3. The method of claim 1, wherein the group R is trifluoromethyl.
  4. 4. The process of claim 1 wherein the transfer hydrogenation catalyst is selected from (Ph 4 C 4 CO) 2 H(μ-H)(CO) 4 Ru 2 、[(4-ClC 6 H 4 ) 4 C 4 CO] 2 H(μ-H)(CO) 4 Ru 2 、[2,5-(C 6 H 4 ) 2 -3,4-(4-MeOC 6 H 4 ) 2 C 4 CO] 2 H(μ-H)(CO) 4 Ru 2 or [2,5-(C 6 H 4 ) 2 -3,4-(4-FC 6 H 4 ) 2 C 4 CO] 2 H(μ-H)(CO) 4 Ru 2 .
  5. 5. The process of claim 1, wherein the transfer hydrogenation catalyst is ((Ph 4 C 4 CO) 2 H(μ-H)(CO) 4 Ru 2 ).
  6. 6. The process of claim 1, wherein the secondary alcohols and corresponding ketones are one or more of propan-2-ol and propan-2-one, butan-2-ol and butan-2-one, pentan-2-ol and pentan-2-one, 3-methylbutan-2-ol and 3-methylbutan-2-one, pentan-3-ol and pentan-3-one, hex-2-ol and hex-2-one, 4-methylpent-2-ol and 4-methylpent-2-one, 3-methylpent-2-ol and 3-methylpent-2-one, 3-dimethylbut-2-ol and 3, 3-dimethylbut-2-one, hex-3-ol and hex-3-one, 2-methylpent-3-ol and 2-methylpent-3-one, and cyclohexanol and cyclohexanone.
  7. 7. The process of claim 1, wherein the secondary alcohol and corresponding ketone are isopropanol and acetone.
  8. 8. The process of claim 1, wherein the conversion of 2, 4-tetramethylcyclobutanedione is at least 50%.
  9. 9. The process of claim 1, wherein the conversion of 2, 4-tetramethylcyclobutanedione is at least 70%.
  10. 10. The process of claim 1, wherein the conversion of 2, 4-tetramethylcyclobutanedione is at least 90%.
  11. 11. The process of claim 1, wherein the selectivity to 2, 4-tetramethylcyclobutane-1, 3-diol is at least 30%.
  12. 12. The process of claim 1, wherein the selectivity to 2, 4-tetramethylcyclobutane-1, 3-diol is at least 60%.
  13. 13. The process of claim 1, wherein the process temperature ranges from 50 ℃ to 300 ℃.
  14. 14. The process of claim 1, wherein the process temperature ranges from 50 ℃ to 200 ℃.
  15. 15. The process of claim 1 wherein the process is carried out under a nitrogen pressure of at least 200 psig to maintain the secondary alcohol in a liquid state.
  16. 16. The method of claim 1, wherein the method time is from 5 minutes to 5 hours.
  17. 17. The process of claim 1, wherein the catalyst concentration is from 0.001 to 10 mole percent based on the concentration of 2, 4-tetramethylcyclobutanedione.
  18. 18. The process of claim 1, wherein the molar ratio of secondary alcohol to 2, 4-tetramethylcyclobutanedione is from 1:1 to 50:1.
  19. 19. The process of claim 1, wherein the molar ratio of secondary alcohol to 2, 4-tetramethylcyclobutanedione is from 1:1 to 20:1.
  20. 20. The process of claim 1, wherein the molar ratio of secondary alcohol to 2, 4-tetramethylcyclobutanedione is from 1:1 to 10:1.

Description

Production of 2, 4-tetramethyl cyclobutane-1, 3-diol from secondary alcohol and 2, 4-tetramethyl cyclobutanedione using homogeneous catalyst Technical Field The present disclosure relates generally to a homogeneously catalyzed process for preparing 2, 4-tetramethylcyclobutane-1, 3-diol (TMCD) by reacting 2, 4-tetramethylcyclobutanedione (dione) with a secondary alcohol. Background Conventionally, 2, 4-tetramethylcyclobutane-1, 3-diol (TMCD) can be produced by hydrogenating 2, 4-tetramethylcyclobutanedione (dione) using a heterogeneous catalyst. In this conventional process, TMCD can be produced by (i) converting isobutyric acid to isobutyric anhydride, (ii) converting isobutyric anhydride to diketones, and (iii) hydrogenating the diketones to TMCD. Hydrogen is required in this conventional process. This process operates at relatively high hydrogen pressures and is limited by the production of many by-products, some of which are produced by acid-catalyzed ring opening of cyclobutane during the hydrogenation process. In the present disclosure, a novel process is disclosed that uses a diketone and a secondary alcohol as starting materials to highly selectively reduce the diketone in a Transfer Hydrogenation (TH) reaction using a ruthenium-containing homogeneous catalyst while co-producing the ketone. In contrast, conventional TH heterogeneous catalysts do not promote such conversion. This new TH process can provide an effective alternative to traditional hydrogenation (with H 2) for the conversion of diketones to TMCD. This new process provides the benefits of (1) this TH process being an inherently safer process (low pressure and without the use of H 2, which is an explosion hazard), (2) cost savings due to reduced use of H 2, (3) lower associated capital costs, (4) significantly fewer byproducts and thus higher yields. Because of the fewer byproducts, TMCD refining can be significantly simplified, requiring less purification. The present disclosure addresses these unmet needs, as well as other needs, as will be apparent from the following description and appended claims. Disclosure of Invention The method of the present disclosure is as set forth in the appended claims. One embodiment of the present disclosure is a process for producing 2, 4-tetramethylcyclobutane-1, 3-diol comprising: (i) Contacting 2, 4-tetramethylcyclobutanedione with a secondary alcohol in the presence of a transfer hydrogenation catalyst to produce 3-hydroxy-2, 4-tetramethylcyclobutanone (ketol) and the corresponding ketone derived from the secondary alcohol, and (Ii) Contacting 3-hydroxy-2, 4-tetramethyl cyclobutanone with a secondary alcohol in the presence of a transfer hydrogenation catalyst to produce 2, 4-tetramethyl cyclobutane-1, 3-diol and a corresponding ketone derived from the secondary alcohol, wherein the ketone is optionally removed by reactive distillation. In one embodiment, the transfer hydrogenation catalyst is a ruthenium complex. In one embodiment, the transfer hydrogenation catalyst is one or more of H2Ru(PPh3)4、Ru3(CO)12、(Ar4C4CO)Ru(CO)3 and (Ar 4C4CO)2H(μ-H)(CO)4Ru2, Wherein (Ar 4C4CO)Ru(CO)3 is represented by the following formula: and Ar is represented by the following general formula: and the radicals R are identical or different and are selected from H, methyl, ethyl, or straight-chain or branched alkyl groups containing 3 to 10 carbon atoms, substituted or unsubstituted aryl groups, carbonyl-containing groups such as ester or amido groups having 2 to 12 carbon atoms, amino groups having 2 to 12 carbon atoms, alkoxy groups having 3 to 10 carbon atoms, nitrile, fluorine, trifluoromethyl or fluorinated hydrocarbon groups such as perfluorobutyl or pentafluorophenyl; and wherein (Ar 4C4CO)2H(μ-H)(CO)4Ru2 is represented by the following general formula: and Ar is represented by the following general formula: And the radicals R are identical or different and are selected from H, methyl, ethyl, or straight-chain or branched alkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted aryl radicals, carbonyl-containing radicals such as ester or amide radicals having 2 to 12 carbon atoms, amino radicals having 2 to 12 carbon atoms, alkoxy radicals having 3 to 10 carbon atoms, nitrile, fluorine, trifluoromethyl or fluorinated hydrocarbon radicals such as perfluorobutyl or pentafluorophenyl radicals. In one embodiment, the transfer hydrogenation catalyst is selected from (Ph4C4CO)2H(μ-H)(CO)4Ru2、[(4-ClC6H4)4C4CO]2H(μ-H)(CO)4Ru2、[2,5-(C6H4)2-3,4-(4-MeOC6H4)2C4CO]2H(μ-H)(CO)4Ru2 or [2,5-(C6H4)2-3,4-(4-FC6H4)2C4CO]2H(μ-H)(CO)4Ru2. In one embodiment, the transfer hydrogenation catalyst is a Shvo catalyst or ((Ph 4C4CO)2H(μ-H)(CO)4Ru2). In one embodiment, the secondary alcohols and corresponding ketones are one or more of propan-2-ol and propan-2-one, butan-2-ol and butan-2-one, pentan-2-ol and pentan-2-one, 3-methylbutan-2-ol and 3-methylbutan-2-one, pentan-3-ol and pentan-3-one, hex-2-ol and hex-2-one, 4-methylp