CN105153008B - A kind of nitrogen compound - Google Patents

A kind of nitrogen compound Download PDF

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Publication number
CN105153008B
CN105153008B CN201510566620.6A CN201510566620A CN105153008B CN 105153008 B CN105153008 B CN 105153008B CN 201510566620 A CN201510566620 A CN 201510566620A CN 105153008 B CN105153008 B CN 105153008B
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nitrogen compound
white crystal
added
cell parameter
compound
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CN105153008A (en
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罗梅
徐佳
张竟成
李学良
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B01J2231/345—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones with organometallic complexes, e.g. by adding ZnR2
    • 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
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrrole Compounds (AREA)

Abstract

A kind of nitrogen compound, its chemical formula is as follows：The synthetic method of the nitrogen compound (I), is to weigh 2.8615g (0.02mol) N (2 ethoxy) succimide to be put into 100mL round-bottomed flasks, adds 50mL absolute methanols and stirring dissolves it；2.3740g (0.01mol) CoCL2 6H2O is added into above-mentioned solution, 48h is heated to reflux；Filtering reacting solution while hot after reaction terminates, filtrate is volatilized naturally, there is white crystal precipitation two days later；White crystal petroleum ether and n-hexane are rinsed 3 times, 30min is dried in vacuo, obtains target product.The nitrogen compound shows preferable catalytic effect as catalyst in the Henle reaction of benzaldehyde, and its conversion ratio is bordering on 100%.

Description

A kind of nitrogen compound
Technical field
The present invention relates to a kind of noval chemical compound and preparation method thereof, more particularly to a kind of nitrogen-containing compound and its preparation side Method, is exactly a kind of heterocycle succinic acid 2, the preparation of the pyrrolidinyl diethyl ester of 5- dicarbapentaborane -1 and its synthetic method.
Background technology
Ester type compound is important medicine intermediate, the existing lot of documents report of its synthetic method【1-4】:
Bibliography：
1.Microwave-Assisted Synthesis of Amide under Solvent-free Conditions,Wang,Xiao-Jian；Yang,Qian；Liu,Fei；You, Qi-Dong, Synthetic Communications(2008),38(7),1028-1035.
2.Highly efficient deacetylation by use of the neutral organotin catalyst[tBu2SnOH(Cl)]2,Orita,Akihiro；Hamada,Yuuki；Nakano,Takehiko；Toyoshima, Shinji；Otera,Junzo Chemistry-A European Journal(2001),7(15),3321-3327.
3.[tBu2SnOH(Cl)]2as a highly efficient catalyst for deacetylation, Orita,Akihiro；Sakamoto,Katsumasa；Hamada,Yuuki；Otera, Junzo, Synlett (2000), (1), 140-142.
4.Study of the resolution of amino acids and amino alcohols in organic solvents,Orsini,F.；Pelizzoni,F.；Ghioni,C.,Amino Acids(1995),9(2),135- 140。
The content of the invention
It is contemplated that for needed for asymmetric syntheses field particularly prepares a kind of effective catalyst of chiral drug offer Compound ligand, technical problem to be solved is to select corresponding raw material and set up corresponding method synthesis of chiral catalyst to match somebody with somebody Body.
(1) chipal compounds alleged by the present invention are the compounds shown in below formula (I)：
Its chemical name：Succinic acid 2, the pyrrolidinyl diethyl ester of 5- dicarbapentaborane -1；
The synthetic method of the compound (I) is without water beetle by N- (2- ethoxys) succimides and cobalt chloride hexahydrate Reacted 48 hours in alcoholic solution, the chemical equation is as follows：
This nitrogen compound (I) synthetic method includes synthesis, separation and purified, and described synthesis is to weigh 2.8615g (0.02mol) N- (2- ethoxys) succimide is put into 100mL round-bottomed flasks, and adding 50mL absolute methanols and stirring makes it Dissolving；2.3740g (0.01mol) CoCL2 6H2O is added into above-mentioned solution, 48h is heated to reflux；Reaction is filtered while hot after terminating Reaction solution, filtrate is volatilized naturally, there is white crystal precipitation two days later；
White crystal petroleum ether and n-hexane are rinsed 3 times, 30min is dried in vacuo, obtains target product.
The reaction mechanism of the reaction can be presumed as follows：
N- (2- ethoxys) succimides are in a large amount of lewis acid CoCl2·6H2Acting in methanol solution for O is produced Succinic acid, then is condensed to form target compound I with raw material N- (2- ethoxys) succimide.
The preparation of this nitrogen compound, using simple, efficient methodology of organic synthesis, one-step synthesis chipal compounds, through X- Diffraction, NMR, IR and elementary analysis determine its structure, and it shows preferably as catalyst in the Henle reaction of benzaldehyde Catalytic effect, its conversion ratio is bordering on 100%.
Brief description of the drawings
Fig. 1 is the single crystal diffraction figure of nitrogen compound (I).
Embodiment
1st, succinic acid 2, the preparation of the pyrrolidinyl diethyl ester of 5- dicarbapentaborane -1
Weigh 2.8615g (0.02mol) N- (2- ethoxys) succinamide to be put into 100mL round-bottomed flasks, add 50mL Absolute methanol and stir dissolve it；2.3740g (0.01mol) CoCL2 6H2O is added into above-mentioned solution, 48h is heated to reflux； Filtering reacting solution while hot after reaction terminates, filtrate is volatilized naturally, there is white crystal precipitation two days later；
White crystal petroleum ether and n-hexane are rinsed 3 times, 30min is dried in vacuo, obtains target product, yield is 20%, 128-130 DEG C of fusing point；1HNMR(600MHz,CDCl3, 27 DEG C), δ (ppm)=4.09 (t, 4H), 2.58 (s, 8H), 2.48 (s,4H),2.41(s,4H),13CNMR(150MHz,CDCl3,27℃)177.8,172.0,60.7,37.1,28.6,28.1；It is red External spectrum data (KBr, cm-1)：3445；2987；2968；2597；2403；2308；1733；1439；1375；1327；1257； 1195；1159；1118；1037；1010；974；961；934；888；822；707；667；609；577；491；HRMS(EI):m/z (%):calcd for C16H20N2O8:368.1220；found:383.1216；
Nitrogen compound crystal data is as follows：
The typical bond distance's data of crystal：
The typical bond angle data of crystal：
2nd, Henle reaction application
0.15mmol complex I (catalytic amount is 20%) is taken in 25mL small flask, add 2 milliliters without water beetle Alcoholic solution, then, 0.1mL benzaldehyde and 0.5mL nitromethane is added into above-mentioned solution, is stirred at room temperature, reaction 24 is small Shi Hou, carries out nmr analysis, conversion ratio：>99%；1H NMR(300MHz,CDCl3) 7.28~7.32 (m, 5H, Ar-H), 5.32 ~5.35 (d, J=9.18Hz, 1H ,-CH), 4.38~4.56 (m, 2H ,-CH2),3.89(br,1H,-OH)。

Claims (1)

1. a kind of synthetic method for having following cell parameter and a nitrogen compound (I) shown in chemical formula, including synthesis and separate, institute The synthesis stated is to weigh 2.8615g (0.02mol) N- (2- ethoxys) succimide to be put into 100mL round-bottomed flasks, is added 50mL absolute methanols and stir dissolve it；2.3740g (0.01mol) CoCL2 6H2O is added into above-mentioned solution, is heated to reflux 48h；Filtering reacting solution while hot after reaction terminates, filtrate is volatilized naturally, there is white crystal precipitation two days later；White crystal is used Petroleum ether and n-hexane are rinsed 3 times, are dried in vacuo 30min, are obtained target product,
The cell parameter of the compound (I) is as follows：At a temperature of 296K, on the X-ray single crystal diffractometer of Oxford, with through graphite The MoK alpha rays of monochromator monochromatizationDiffraction data is collected with ω-θ scan modes, it is characterised in that crystal Belong to orthorhombic system, space group Pbcn, cell parameterα=90 °；β=90 °；γ=90 °.
CN201510566620.6A 2015-09-08 2015-09-08 A kind of nitrogen compound Active CN105153008B (en)

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Graft copolymerization of N-vinyl imides to preirradiated polyethylene film and the preparation of anion-exchange membranes from the resulting graft copolymers;Murata Kenichi;《Nippon Kagaku Kaishi》;19721231;第10卷;1949-1953页，尤其2.1.1、3部分 *
Mechanism of Formation of Heat Stable Salts (HSSs) and their Roles in Further Degradation of Monoethanolamine during CO2 Capture from Flue Gas Streams;Teeradet Supap，等;《Energy Procedia》;20111231;591-598页 *
丁二酸合成研究进展;薛锋;《安徽化工》;20091031;第35卷(第5期);全文 *

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