公开(公告)号：WO2017222532A1

公开(公告)日：2017-12-28

申请号：PCT/US2016/039005

申请日：2016-06-23

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth

IPC: C07D307/08 ,  C07D307/12

CPC classification number: C07D307/12 ,  C07D307/06 ,  C07D307/10 ,  C07D307/18 ,  C07D307/22 ,  C07D307/24 ,  C07D307/36

Abstract: A process for the preparation of diastereomeric mono- and 2,5- bis(halomethyl)tetrahydrofurans from renewable THF-diols is described. Also disclosed are certain derivative compounds that can be prepared from the mono or di-alkyl halide furanic compounds.

Abstract translation: 描述了由可再生的THF-二醇制备非对映异构单 - 和2,5-双（卤代甲基）四氢呋喃的方法。 还公开了可由单烷基卤化物呋喃化合物或二烷基卤化物化合物制备的某些衍生化合物。

公开(公告)号：WO2017091435A1

公开(公告)日：2017-06-01

申请号：PCT/US2016/062481

申请日：2016-11-17

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： HAGBERG, Erik ,  HOWARD, Stephen J. ,  STENSRUD, Kenneth

IPC: C08L67/02 ,  B29C47/88

CPC classification number: B29B7/002 ,  B01J31/00 ,  B29B7/88 ,  C07D307/68

Abstract: A method for preparing sugar-based oligomers is described. The process involves sequential (one-pot) esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol and transesterification with a glycol, as catalyzed by relatively low loadings of homogeneous organometallic Lewis acids, which can be retained in the product mixture from the esterification through transesterification.

Abstract translation: 描述了制备糖基低聚物的方法。 该方法包括用醇对2,5-呋喃 - 二羧酸（FDCA）进行连续（一锅法）酯化并与二醇进行酯交换，由相对低量的均相有机金属路易斯酸催化，其可保留在产物中 通过酯交换进行酯化的混合物。

公开(公告)号：WO2017065980A1

公开(公告)日：2017-04-20

申请号：PCT/US2016/054278

申请日：2016-09-29

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  SMITH, Brennan

IPC: C07C1/22 ,  C07D307/48 ,  C07D405/06

CPC classification number: C07D307/48

Abstract: Methods for preparing 1) a sugar-derived ester, 2) a glycol generated from reduction of the ester, and 3) polymers fabricated from polycondensation of the ester or glycol with various diamines and dicarboxylic acids are described. In particular, the ester is levulinic 5-methyl-2-furfural (LMF), the acylation product of hydroxymethyl-furfural (HMF) and either a levulinyl halide or levulinic acid. Each of the embodiments for the synthesis is highly selective for the product and can be executed under relatively mild reaction conditions.

Abstract translation: 描述了制备1）糖衍生酯，2）由酯还原产生的二醇和3）由酯或二醇与各种二胺和二羧酸缩聚制备的聚合物的方法 。 特别地，酯是乙酰丙酸5-甲基-2-糠醛（LMF），羟甲基糠醛（HMF）的酰化产物和乙酰丙酰卤或乙酰丙酸。 合成的每个实施方案对产物都是高度选择性的，并且可以在相对温和的反应条件下进行。

公开(公告)号：WO2016099789A1

公开(公告)日：2016-06-23

申请号：PCT/US2015/061559

申请日：2015-11-19

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  VENKITASUBRAMANIAN, Padmesh ,  MA, Chi-cheng

IPC: C07D493/04

CPC classification number: C07C68/06 ,  C07C41/16 ,  C07C43/10 ,  C07C43/12 ,  C07C68/04 ,  C07D307/12 ,  C07D307/42 ,  C07D493/04 ,  C07C43/13

Abstract: A method of etherifying glycols or other diols by employing renewable reagents is disclosed. In particular, the method involves contacting a diol with an alkylating agent in an alcoholic solvent, catalyzed with a catalyst (carbonic acid) generated in situ (from CO 2 ). The mono- and di-ether products can serve as valued precursors to an array of renewable surfactants, dispersants, and lubricants, among others.

Abstract translation: 公开了通过使用可再生试剂醚化二醇或其它二醇的方法。 特别地，该方法包括使二醇与烷基化试剂在醇溶剂中接触，用原位生成的催化剂（碳酸）（由CO 2）催化。 单醚和二醚产品可以作为可再生表面活性剂，分散剂和润滑剂等的一系列重要前体。

公开(公告)号：WO2015156839A1

公开(公告)日：2015-10-15

申请号：PCT/US2014/066298

申请日：2014-11-19

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth ,  HAGBERG, Erik

IPC: C07D493/04

CPC classification number: C07D307/12 ,  A23L27/34 ,  A23V2002/00 ,  B01J23/72 ,  B01J25/00 ,  C07C29/132 ,  C07C29/60 ,  C07D307/20 ,  C07D493/04 ,  C07G3/00 ,  C07C31/24 ,  C07C31/22 ,  C07C31/26

Abstract: A process for preparing materials derived from sugar alcohols such that the dehydration products exhibit better accountability and improved color to water-clear or near water-white appearance is described. In particular, the process involves employing a reducing Brnsted acid (e.g., phosphonic acid) for the catalysis of sugar alcohols to their corresponding dehydrated-cyclized products.

Abstract translation: 描述了制备衍生自糖醇的材料的方法，使得脱水产物表现出更好的问题性和改善的颜色至透明或接近水白色外观。 特别地，该方法包括使用还原布朗斯台德酸（例如膦酸）来将糖醇催化成相应的脱水环化产物。

公开(公告)号：WO2014179156A1

公开(公告)日：2014-11-06

申请号：PCT/US2014/035395

申请日：2014-04-25

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth

IPC: C07D307/48

CPC classification number: C07D307/46 ,  C07C51/41 ,  C07D307/48 ,  C07D307/52 ,  C07D307/54

Abstract: 5-(hydroxymethyl) furan-2-carbaldehyde (HMF)-sulfonates and a method of preparing the same are described. The method involves reacting a mixture of 5-(hydroxymethyl)furfural (HMF), with at least one of a) a trifluoromethanesulfonate anhydride (triflate), b) a p -toluene-sulfonyl halide (tosylate), and c) methane-sulfonyl halide (mesylate), and a reagent of either 1) a nucleophilic base or 2) a combination of a non-nucleophilic base and a nucleophile. The HMF-sulfonates (e.g., triflate, tosylate, mesylate, etc. analogs of HMF) can serve as precursor materials from which various derivative compounds can be synthesized.

Abstract translation: 描述了5-（羟甲基）呋喃-2-甲醛（HMF） - 磺酸盐及其制备方法。 该方法包括使5-（羟甲基）糠醛（HMF）与a）三氟甲磺酸酐（三氟甲磺酸酯），b）对甲苯磺酰卤（甲苯磺酸酯）中的至少一种和c）甲磺酰基 卤化物（甲磺酸酯）和1）亲核碱的试剂或2）非亲核碱和亲核试剂的组合。 HMF-磺酸盐（例如，HMF的三氟甲磺酸酯，甲苯磺酸酯，甲磺酸酯等）类似物可以用作可以合成各种衍生化合物的前体材料。

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：WO2014137576A1

公开(公告)日：2014-09-12

申请号：PCT/US2014/016758

申请日：2014-02-18

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth

IPC: C07D493/04 ,  A61K31/424

CPC classification number: C07D493/04 ,  C07D519/00

Abstract: Isohexide monotriflate compounds and a method of preparing the same are described. The method involves reacting a mixture of an isohexide, a trifluoromethanesulfonate anhydride, and either 1) a nucleophilic base or 2) a combination of a non-nucleophilic base and a nucleophile. The isohexide monotriflate compounds can serve as precursor materials from which various derivative compounds can be synthesized.

Abstract translation: 描述了异己烯单萜化合物及其制备方法。 该方法包括使异丙醚，三氟甲烷磺酸酐和1）亲核碱或2）非亲核碱和亲核试剂的组合的混合物反应。 异己烯单萜化合物可以作为可以合成各种衍生化合物的前体材料。

公开(公告)号：WO2013188253A1

公开(公告)日：2013-12-19

申请号：PCT/US2013/044878

申请日：2013-06-10

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： STENSRUD, Kenneth

IPC: C07D493/04 ,  C07D407/14

CPC classification number: C07D493/04

Abstract: An improved, high yielding process is disclosed for making bisglycidyl ether derivatives of isosorbide, isomannide and/or isoidide, wherein up to quantitative yields overall are demonstrated. In another related aspect, a process is disclosed for making novel monoallyl, monoglycidyl ether derivatives or a combination of monoallyl, monoglycidyl ether derivatives and bisglycidyl ether derivatives via the same diallyl isohexide intermediate.

Abstract translation: 公开了一种改进的高产率方法，用于制备异山梨醇，异烟肼和/或异氰酸酯的双缩水甘油醚衍生物，其中总体上达到定量产率。 在另一相关方面，公开了通过相同的二烯丙基异己烯中间体制备新的单烯丙基，单缩水甘油醚衍生物或单烯丙基，单缩水甘油醚衍生物和双缩水甘油醚衍生物的组合的方法。

公开(公告)号：WO2021231556A1

公开(公告)日：2021-11-18

申请号：PCT/US2021/031969

申请日：2021-05-12

Applicant: ARCHER DANIELS MIDLAND COMPANY

Inventor： INGRAM, Andrew ,  HAGBERG, Erik ,  MA, Chi-Cheng ,  MCCLURG, Jessica ,  STENSRUD, Kenneth

IPC: C07D307/68 ,  C07D307/46 ,  C07C51/16 ,  C07C55/02

Abstract: Processes for the oxidation of carbohydrate dehydration products, such as furanics that can be oxidized to the bio-based monomer 2,5-furandicarboxylic acid (FDCA), are disclosed, according to which certain co-feeds, having been discovered to impart a beneficial reaction stabilizing effect, are oxidized together with the carbohydrate dehydration products. This can advantageously counteract, in whole or in part, detrimental effects of humin impurities present in oxidation feed, with such impurities having been generated as byproducts of the upstream dehydrating step. An important co-feed is para-xylene that can be co-oxidized to form the petroleum-based monomer terephthalic acid (TPA), such that co-processing can beneficially yield two valuable monomers, while improving performance, particularly in terms of reaction stability, over comparable processes in which only the first monomer is produced. Related aspects involve opportunities for retrofitting existing monomer production facilities to enable co-processing of carbohydrate dehydration products that can lead to the above-noted advantages.