CN109384643B - Method for preparing sorbitol - Google Patents

Method for preparing sorbitol Download PDF

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CN109384643B
CN109384643B CN201710683921.6A CN201710683921A CN109384643B CN 109384643 B CN109384643 B CN 109384643B CN 201710683921 A CN201710683921 A CN 201710683921A CN 109384643 B CN109384643 B CN 109384643B
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reaction
sorbitol
transition metal
isopropanol
metal catalyst
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CN109384643A (en
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李峰
王荣周
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a method for preparing sorbitol, which utilizes transition metal catalysis, uses isopropanol as a hydrogen source to synthesize the sorbitol, uses cheap and environment-friendly isopropanol as the hydrogen source and a solvent, and has the advantages of high yield, environment friendliness and the like, so the reaction has important development significance.

Description

Method for preparing sorbitol
Technical Field
The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a method for preparing sorbitol.
Background
Sorbitol is an important compound, widely exists in fruits of natural plants, and can be used as food moisturizer, aroma-keeping agent, antioxidant, cosmetic raw material, cigarette, toothpaste humectant, raw material of adhesive, diuretic and choleretic drug, etc. For example, in polyether production, sorbitol serves as an initiator; in the pharmaceutical industry, sorbitol is mainly used for the production of vitamin C. (a) Takeda, t.; takeda, s.; kakigi A. Auris Nasus Larynx.2009,36, 146-; (b) ayorinde, f.o.; gelain, s.v.; johnson, J.H.Rapid.Commu.Mass.Spec,2000,14, 2116-2124; (c) katarzyna, g.; sylwestern, G.J.Bio, mater.Res.2006,79, 128-138; (a) lee, c.h.; takagi, h.; okamoto, H.J.Poly.Sci.part.a-Poly.chem.2009,47,6025-6031.
The traditional methods for preparing sorbitol mainly include catalytic reduction, electrolytic oxidation and fermentation. (a) Huangyangwang, Ningwensheng, Li Xiaonian Zhejiang chemical, 2001,32, 51-52; (b) luzhangguang, luyuhua, proceedings of the national institute of chemical engineering of yan-Qingdao, 2003,23, 44-47; (c) zhujianlang, Wuzhengxing chemical engineering journal, 2006,20,47-51.
In recent years, the reduction method adopted for preparing sorbitol at home and abroad is mainly high-pressure catalytic hydrogenation, and although the method has a plurality of advantages, hydrogen is used in the reaction process, so that the safety coefficient is low. (a) Barbaro, p.; liguori, f.; Moreno-Marrodan, C.Green chem.2016,18, 2935-2940; (b) guo, x.; wang, x.; guan, j.; chen, x.; qin, z.; mu, X.; xian, m.chi.j.catal.2014, 35, 733-; (c) perrard, a.; gallezot, p.; joly, j.p.; durand, r.; baljou, c.; coq, b.; trens, P.App.Catal.A, Gen.2007.331, 100-104; (d) mathew, k.m.; ravi, s.; padmanabhan, d.; unny, v.k.p.; sivaprasad, N.J.Lab.Compd.radiopharm.2006,49, 333-.
Therefore, from the perspective of organic synthesis, a new class of organometallic catalysts has been developed, which are capable of catalyzing such reactions in a more environmentally friendly and mild state by using inexpensive, safe, and non-toxic isopropanol as a hydrogen source and solvent, and thus are of great significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing sorbitol.
The invention is realized by the following technical scheme: a process for the preparation of sorbitol (formula I),
Figure BDA0001376185800000011
from glucose monohydrate (formula II)
Figure BDA0001376185800000012
And carrying out hydrogenation reaction to generate the target product.
The reaction takes place in the presence of a transition metal catalyst and has the general formula
Figure BDA0001376185800000021
The method for synthesizing the sorbitol is realized by the following specific steps:
adding glucose monohydrate, a transition metal catalyst iridium complex and a solvent isopropanol into a reaction vessel; the reaction mixture was heated in an oil bath, after several hours of reaction, cooled to room temperature and the solvent was removed by rotary evaporation to give the title compound.
Further, in the reaction, the complex structure of iridium is:
Figure BDA0001376185800000022
further, in the reaction, the amount of the iridium complex used was 0.2 mol% based on the glucose monohydrate.
Further, in the reaction, the reaction time is not less than 12 hours.
Further, in the reaction, the reaction temperature is not lower than 120 ℃.
Compared with the prior art, the method takes the glucose monohydrate as the raw material, takes the isopropanol as the hydrogen source and the solvent, and generates the sorbitol by hydrogen transfer in the presence of the transition metal catalyst. The reaction exhibits two significant advantages: 1) cheap, safe and nontoxic isopropanol is used; 2) the reaction atom has high economy; therefore, the reaction meets the requirement of green chemistry and has wide development prospect.
Detailed Description
The following examples are shown to illustrate certain embodiments of the present invention and should not be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.
EXAMPLE 1 sorbitol
Sorbitol
Figure BDA0001376185800000023
Mixing glucose monohydrate (198mg,1.0mmol) and cat [ Ir ]](1.1mg,0.002mmol,0.2 mol%) and isopropanol (5mL) were added sequentially to a 25mL Kjeldahl tube, N2Protecting, and reacting at 120 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 92 percent of
1H NMR(500MHz,CDCl3)δ4.54(d,J＝4.6Hz,1H),4.47-4.45(m,2H),4.38(d,J＝5.8Hz,1H),4.31(t,J＝5.6Hz,1H),4.10(d,J＝6.7Hz,1H),3.67-3.66(m,1H),3.59-3.52(m,2H),3.47-3.44(m,2H),3.39-3.33(m,3H).13C NMR(125MHz,CDCl3)δ73.8,72.3,71.5,68.9,63.5,62.6.。

Claims (5)

1. A process for the preparation of sorbitol I, characterized in that,
Figure FDA0003035923520000011
glucose monohydrate II in the presence of transition metal catalyst,
Figure FDA0003035923520000012
generating the target product through hydrogenation reaction;
wherein, the transition metal catalyst is an iridium complex compound, and the structure thereof is as follows:
Figure FDA0003035923520000013
2. the method of claim 1, wherein the transition metal catalyst is present in an amount of 0.2 mol% of the glucose monohydrate.
3. The method of claim 1, wherein the reaction time is not less than 12 hours.
4. The process of claim 1, wherein the reaction temperature is not less than 120 ℃.
5. The process of claim 1, wherein the reaction is carried out in the presence of the solvent isopropanol.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203892A (en) * 2012-02-23 2014-12-10 关东化学株式会社 Dehydrogenation catalyst, and carbonyl compound and hydrogen production method using said catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203892A (en) * 2012-02-23 2014-12-10 关东化学株式会社 Dehydrogenation catalyst, and carbonyl compound and hydrogen production method using said catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Catalytic hydrogenation of fine chemicals: sorbitol production;K.van Gorp 等;《Catalysis Today》;19991117;第52卷;第357页 Table 8 *
Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone;Ryoko Kawahara 等;《Angew.Chem.Int.Ed.》;20121107;第51卷;第12794-12790页 *
RuC12(PPh3)3-catalyzed transfer hydrogenation of D-glucose;S.Rajagopal 等;《Journal of Molecular Catalysis》;19920915;第75卷;第199-209页 *

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