公开(公告)号：WO2014137619A1

公开(公告)日：2014-09-12

申请号：PCT/US2014/017563

申请日：2014-02-21

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: C12G3/08 ,  C13K13/00

CPC classification number: C07D493/04

Abstract: A process is described for the acid-catalyzed dehydration of a sugar alcohol, wherein the catalyst comprises a water-tolerant Lewis acid. In particular embodiments, the catalyst comprises a homogeneous water-tolerant Lewis acid, especially a homogeneous Lewis acid selected from the group consisting of bismuth (III) triflate, gallium (III) triflate, scandium (III) triflate, aluminum triflate, tin (II) triflate and indium (III) triflate. Such catalysts are effective for dehydrating both of sorbitol and the 1,4-sorbitan dehydration precursor of isosorbide, and bismuth (III) triflate particularly is beneficial for dehydrating mannitol to isomannide.

Abstract translation: 描述了用于糖醇的酸催化脱水的方法，其中所述催化剂包含耐水路易斯酸。 在特定实施方案中，催化剂包含均相耐水路易斯酸，特别是选自三氟甲磺酸铋（III），三氟甲磺酸镓（III），三氟甲磺酸钪（III），三氟甲磺酸铝，二（二 ）三氟甲磺酸盐和铟（III）三氟甲磺酸盐。 这种催化剂对山梨糖醇和异山梨醇的1,4-脱水山梨糖醇脱水前体的脱水是有效的，并且三氟甲磺酸铋（III）特别有利于将甘露糖醇脱水成异麦芽糖苷。

公开(公告)号：WO2015094895A1

公开(公告)日：2015-06-25

申请号：PCT/US2014/069701

申请日：2014-12-11

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: C07D493/04 ,  C08G63/12

CPC classification number: C07D493/04 ,  B01J31/0232 ,  B01J2231/49 ,  B01J2531/004

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method can enable direct alcohol acylation with carboxylic acids. In particular, the method involves reacting an isohexide and an excess of carboxylic acid, in the presence of a water-tolerant Lewis acid catalyst. Water-tolerant Lewis aid catalysts can furnish relatively high diester yields (e.g., ≥ 55%-60%) at lower catalyst loads. This feature, among others, is highly desirable for cost savings, and can improve process economics.

Abstract translation: 描述了用于酸性催化酰化异己烯酯的方法。 该方法可以实现与羧酸的直接醇酰化。 特别地，该方法包括在耐水性路易斯酸催化剂存在下使异己烯醚和过量的羧酸反应。 耐水Lewis助催化剂可以在较低的催化剂负载下提供较高的二酯产率（例如≥55％-60％）。 这一特性尤其适用于节省成本，并且可以提高工艺经济性。

公开(公告)号：WO2015094894A1

公开(公告)日：2015-06-25

申请号：PCT/US2014/069698

申请日：2014-12-11

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  ROCKAFELLOW, Erin M.

IPC: C07D493/04 ,  A61K31/424

CPC classification number: C07D493/04

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method involves a reaction of an isohexide and an excess of carboxylic acid in the presence of a Lewis acid or a Brnsted acid catalyst. One or more Lewis acid or Brnsted acid can faciliate conversion of isohexides to their corresponding mono and diesters with a pronounced greater regio-selectivity of exo- OH over endo -OH of the isohexide in the product. Particular catalytic acid species include zirconium chloride (ZrCl 4 ) and phosphonic acid (H 3 PO 3 ), which manifest a ratio of exo:endo regioselectivity of about 5.0≠.3:1and about 4.00.3:1, respectively.

Abstract translation: 描述了用于酸性催化酰化异己烯酯的方法。 该方法包括在路易斯酸或布朗斯台德酸催化剂存在下异丙醚和过量的羧酸的反应。 一种或多种路易斯酸或布朗斯台德酸可以将异己烯酯转化成其相应的单酯和二酯，其中外OH的显着更大的区域选择性超过产物中异己烯的内-OH。 特别的催化酸性物质包括氯化锆（ZrCl 4）和膦酸（H 3 PO 3），其分别表现出约5.0≠.3：1和约4.00.3：1的外向内区域选择性比。

公开(公告)号：EP2964743B1

公开(公告)日：2018-09-05

申请号：EP14759625.8

申请日：2014-02-21

Applicant: Archer-Daniels-Midland Company

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: C12G3/08 ,  C13K13/00

CPC classification number: C07D493/04

Abstract: A process is described for the acid-catalyzed dehydration of a sugar alcohol, wherein the catalyst comprises a water-tolerant Lewis acid. In particular embodiments, the catalyst comprises a homogeneous water-tolerant Lewis acid, especially a homogeneous Lewis acid selected from the group consisting of bismuth (III) triflate, gallium (III) triflate, scandium (III) triflate, aluminum triflate, tin (II) triflate and indium (III) triflate. Such catalysts are effective for dehydrating both of sorbitol and the 1,4-sorbitan dehydration precursor of isosorbide, and bismuth (III) triflate particularly is beneficial for dehydrating mannitol to isomannide.

公开(公告)号：EP3083637A1

公开(公告)日：2016-10-26

申请号：EP14872425.5

申请日：2014-12-11

Applicant: Archer Daniels Midland Company

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: C07D493/04 ,  C08G63/12

CPC classification number: C07D493/04 ,  B01J31/0232 ,  B01J2231/49 ,  B01J2531/004

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method can enable direct alcohol acylation with carboxylic acids. In particular, the method involves reacting an isohexide and an excess of carboxylic acid, in the presence of a water-tolerant Lewis acid catalyst. Water-tolerant Lewis aid catalysts can furnish relatively high diester yields (e.g., ≥ 55%-60%) at lower catalyst loads. This feature, among others, is highly desirable for cost savings, and can improve process economics.

Abstract translation: 描述了用于异己糖醇酸催化酰化的方法。 该方法可以使羧酸直接进行醇酰化。 特别地，该方法涉及在耐水路易斯酸催化剂存在下使异己糖醇和过量的羧酸反应。 耐水路易斯助催化剂可以在较低的催化剂负荷下提供较高的二酯收率（例如，≥55％-60％）。 除此之外，这一特征非常适合节省成本，并且可以提高工艺经济性。

公开(公告)号：EP2968255A1

公开(公告)日：2016-01-20

申请号：EP14773375.2

申请日：2014-02-25

Applicant: Archer Daniels Midland Company

Inventor： SANBORN, Alexandra ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: A61K31/341 ,  A61K31/70 ,  A61K9/08 ,  A61K47/30

CPC classification number: C07D307/48 ,  A61K9/08 ,  A61K31/341 ,  A61K47/10 ,  C07D307/46 ,  C07D307/50 ,  C09K15/06

Abstract: Disclosed is a process for making HMF′ or a derivative of HMF by dehydrating one or more hexose sugars in a reduced oxygen environment, in another, related aspect, a method for improving the stability and resistance to degradation of an HMF product Involves adding one or more antioxidants to the HMF product.

公开(公告)号：EP2964743A1

公开(公告)日：2016-01-13

申请号：EP14759625.8

申请日：2014-02-21

Applicant: Archer-Daniels-Midland Company

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: C12G3/08 ,  C13K13/00

CPC classification number: C07D493/04

Abstract: A process is described for the acid-catalyzed dehydration of a sugar alcohol, wherein the catalyst comprises a water-tolerant Lewis acid. In particular embodiments, the catalyst comprises a homogeneous water-tolerant Lewis acid, especially a homogeneous Lewis acid selected from the group consisting of bismuth (III) triflate, gallium (III) triflate, scandium (III) triflate, aluminum triflate, tin (II) triflate and indium (III) triflate. Such catalysts are effective for dehydrating both of sorbitol and the 1,4-sorbitan dehydration precursor of isosorbide, and bismuth (III) triflate particularly is beneficial for dehydrating mannitol to isomannide.

公开(公告)号：EP2968255B1

公开(公告)日：2018-12-05

申请号：EP14773375.2

申请日：2014-02-25

Applicant: Archer Daniels Midland Company

Inventor： SANBORN, Alexandra ,  HAGBERG, Erik ,  HOWARD, Stephen ,  ROCKAFELLOW, Erin M.

IPC: A61K31/341 ,  A61K31/70 ,  A61K9/08 ,  A61K47/30

CPC classification number: C07D307/48 ,  A61K9/08 ,  A61K31/341 ,  A61K47/10 ,  C07D307/46 ,  C07D307/50 ,  C09K15/06

Abstract: Disclosed is a process for making HMF′ or a derivative of HMF by dehydrating one or more hexose sugars in a reduced oxygen environment, in another, related aspect, a method for improving the stability and resistance to degradation of an HMF product Involves adding one or more antioxidants to the HMF product.

公开(公告)号：EP3083636B1

公开(公告)日：2018-09-05

申请号：EP14871941.2

申请日：2014-12-11

Applicant: Archer Daniels Midland Company

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  ROCKAFELLOW, Erin M.

IPC: C07D493/04 ,  A61K31/424

CPC classification number: C07D493/04

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method involves a reaction of an isohexide and an excess of carboxylic acid in the presence of a Lewis acid or a Brnsted acid catalyst. One or more Lewis acid or Brnsted acid can facilitate conversion of isohexides to their corresponding mono and diesters with a pronounced greater regio-selectivity of exo-OH over endo-OH of the isohexide in the product. Particular catalytic acid species include zirconium chloride (ZrCl4) and phosphonic acid (H3PO3), which manifest a ratio of exo:endo regioselectivity of about 5.0≠3:1 and about 4.00.3:1, respectively.

公开(公告)号：EP3083636A1

公开(公告)日：2016-10-26

申请号：EP14871941.2

申请日：2014-12-11

Applicant: Archer Daniels Midland Company

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik ,  ROCKAFELLOW, Erin M.

IPC: C07D493/04 ,  A61K31/424

CPC classification number: C07D493/04

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method involves a reaction of an isohexide and an excess of carboxylic acid in the presence of a Lewis acid or a Brønsted acid catalyst. One or more Lewis acid or Brønsted acid can facilitate conversion of isohexides to their corresponding mono and diesters with a pronounced greater regio-selectivity of exo-OH over endo-OH of the isohexide in the product. Particular catalytic acid species include zirconium chloride (ZrCl4) and phosphonic acid (H3PO3), which manifest a ratio of exo:endo regioselectivity of about 5.0≠3:1 and about 4.00.3:1, respectively.