CN107674004A - A kind of synthetic method and purposes of acetylurea dimer crystalline compounds - Google Patents

A kind of synthetic method and purposes of acetylurea dimer crystalline compounds Download PDF

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CN107674004A
CN107674004A CN201710975450.6A CN201710975450A CN107674004A CN 107674004 A CN107674004 A CN 107674004A CN 201710975450 A CN201710975450 A CN 201710975450A CN 107674004 A CN107674004 A CN 107674004A
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acetylurea
dimer
crystalline compounds
reaction
synthetic method
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罗梅
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Hefei Xiangchen Chemical Engineering Co Ltd
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Hefei Xiangchen Chemical Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
    • C07C275/48—Y being a hydrogen or a carbon atom
    • C07C275/50—Y being a hydrogen or an acyclic carbon atom
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0249—Ureas (R2N-C(=O)-NR2)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • 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
    • 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

Abstract

A kind of acetylurea dimer compound, its chemical formula are as follows：

Description

A kind of synthetic method and purposes of acetylurea dimer crystalline compounds
First, technical field
The present invention relates to a kind of compound and preparation method thereof, more particularly to a kind of nitrogen-containing compound and preparation method thereof, definitely It is a kind of synthetic method of acetylurea dimer crystalline compounds that ground, which is said,.
2nd, background technology
Acetyl carbamide compound is important medicine intermediate, its synthetic method and the existing document report of application【1-3】
Bibliography：
1. Acetylcarbamide complexes of some lanthanide bromides and chlorides: Syntheses and structures
Alikberova, L. Yu.; Al'bov, D. V.; Bushmeleva, A. S.; Fedorova, G. A.; Kravchenko, V. V., Russian Journal of Coordination Chemistry (2014), 40 (12), 918-924.
2. New method of preparing N- acetylurea, Kurbanova, M. M. Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya (2004), 47 (8), 165.
3. Crystallographic characterization of monoacylated ureas, Hartung, Helmut; Lux, Georg; Hennicke, Rainer;Schellenberger, Alfred, Zeitschrift fuer Chemie (1973), 13 (6), 234-235.
3rd, the content of the invention
It is contemplated that medicine is particularly prepared for organic synthesis field provides a kind of compound ligand needed for effective catalyst, Technical problem to be solved is to select corresponding raw material and establish corresponding method synthetic catalyst part.
(1) compound alleged by the present invention is the compound shown in below formula (I)：
Its chemical name：Acetylurea dimer.
The compound（Ⅰ）Synthetic method be that a cyano group propenyl benzene and acetylurea are molten in catalyst zinc chloride and absolute methanol Reacted in liquid,
The chemical equation is as follows：
This acetylurea dimer compound (I) synthetic method includes synthesis, separation and purifying, and described synthesis is anhydrous and oxygen-free bar Under part, 0.6420g is weighed（0.005mol）Zinc chloride, acetylurea 1.0046g and a cyano group propenyl benzene 1.3275g are put into In two mouthfuls of flasks of 100mL, adding 20mL absolute methanols and being stirred at room temperature makes its dissolving；After reaction 48 hours, heat filtering, dichloro is added Methane and absolute ethyl alcohol, and solution is volatilized naturally, obtain white crystal.
The reaction mechanism of the reaction can be presumed as follows：
Intermolecular polymerization shape occurs for acetylurea acetylurea in the presence of absolute methanol, a cyano group propenyl benzene and catalyst zinc chloride Into target compound I.
The preparation of this acetylurea dimer compound (I), using simple, efficient methodology of organic synthesis, one-step synthesis, warp X- diffraction, NMR, IR and elementary analysis determine its structure, its as catalyst benzaldehyde nitrile silicification reaction and pyruvic acid second Certain catalytic effect is shown in the Henle reaction of ester, its conversion ratio is respectively up to 18% and 86%.
4th, illustrate
Fig. 1 is the single crystal diffraction figure of acetylurea dimer compound (I).
5th, embodiment
The preparation of acetylurea dimer compound (I)
Weigh 0.6420g（0.005mol）Zinc chloride, acetylurea 1.0046g and a cyano group propenyl benzene 1.3275g are put into 100mL circles In the flask of bottom, add after 48h is stirred at room temperature in 30mL absolute methanols and stop reaction heat filtering, add dichloromethane and absolute ethyl alcohol, And solution volatilizees naturally, obtain white crystal；Yield is 58%, 215-217 °C of fusing point；Elemental analysis data C6H12N4O4, C： 35.29%； H：5.92%；N：27.44%；Measured value：C 35.53%； H：5.71%；N：27.72%；HRMS (e/m) theoretical value： 204.0859;Measured value：204.0843;1HNMR (600MHz, CDCl3, 27℃), δ (ppm) = 10.12(s, 1H), 7.89-7.91(m, 1H), 6.81(s, 1H), 2.0(s, 3H); 13C NMR (150 MHz, CDCl3) 170.8, 153.2, 22.4；Ir data (KBr, cm-1)：3379,3333,3230,1691,1671,1417, 1370, 1256, 1099, 1034, 943, 875, 813, 699, 570, 451;
Nitrogen compound crystal data is as follows：
Empirical formula C6H12N4O4
Molecular weight 204.20
Temperature 293 (2) K
Wavelength 0.71073
Crystallographic system, Space group Monoclinic system, P21
Cell parameter a=7.012 (3) α=90 °
b = 5.088(3) Å β = 98.208(10)°.
c = 13.674(7) Å γ = 90 °
Volume 482.9（4）Å^3
Charge density 2,1.404Mg/m^3
The mm^-1 of absorption correction parameter 0.118
Number of electrons 216 in unit cell
The 70x 0.140x 0.100mm of crystal size 0.1
The to 24.999 of scope 1.505 at Theta angles
HKL index capture range -8<=h<=6, -6<k<=6, -15<l<=16
Collection/independent diffraction data 2592/ 1619 [R (int)=0.0203]
The method Multi Slice Mode of absorption correction
The Matrix least square method for the method F^2 that refine uses
Number/number of parameters 1619/7/129 of data number/use limitation
The method 1.901 that refine uses
The uniformity factor R 1=0.1269 of point diffraction, ω R2=0.4180
The identical factor R 1=0.1438 of observable diffraction, ω R2=0.4487
And -0.866 e. the ^-3 of maximum summit and peak valley 0.744 on difference Fourier figure
The typical bond distance's data of crystal：
N(1)-C(3) 1.314(14)
N(1)-H(1A) 0.8600
N(1)-H(1B) 0.8600
N(2)-C(1) 1.346(18)
N(2)-C(3) 1.398(11)
N(2)-H(2) 0.8600
N(3)-C(6) 1.213(16)
N(3)-H(3A) 0.8600
N(3)-H(3B) 0.8600
N(4)-C(4) 1.307(19)
N(4)-C(6) 1.552(16)
N(4)-H(4) 0.8600
O(1)-C(1) 1.169(17)
O(2)-C(3) 1.209(13)
O(3)-C(6) 1.225(14)
O(4)-C(4) 1.34(2)
C(1)-C(2) 1.505(17)
C(2)-H(2A) 0.9600
C(2)-H(2B) 0.9600
C(2)-H(2C) 0.9600
C(4)-C(5) 1.429(16)
C(5)-H(5A) 0.9600
C(5)-H(5B) 0.9600
C(5)-H(5C) 0.9600
The typical bond angle data of crystal：
C(3)-N(1)-H(1A) 120.0
C(3)-N(1)-H(1B) 120.0
H(1A)-N(1)-H(1B) 120.0
C(1)-N(2)-C(3) 134.7(14)
C(1)-N(2)-H(2) 112.6
C(3)-N(2)-H(2) 112.7
C(6)-N(3)-H(3A) 120.0
C(6)-N(3)-H(3B) 120.0
H(3A)-N(3)-H(3B) 120.0
C(4)-N(4)-C(6) 125.0(14)
C(4)-N(4)-H(4) 117.5
C(6)-N(4)-H(4) 117.5
O(1)-C(1)-N(2) 119.1(12)
O(1)-C(1)-C(2) 129.0(13)
N(2)-C(1)-C(2) 111.8(11)
C(1)-C(2)-H(2A) 109.5
C(1)-C(2)-H(2B) 109.4
H(2A)-C(2)-H(2B) 109.5
C(1)-C(2)-H(2C) 109.5
H(2A)-C(2)-H(2C) 109.5
H(2B)-C(2)-H(2C) 109.5
O(2)-C(3)-N(1) 123.2(7)
O(2)-C(3)-N(2) 120.2(11)
N(1)-C(3)-N(2) 116.6(11)
N(4)-C(4)-O(4) 123.3(11)
N(4)-C(4)-C(5) 121.2(15)
O(4)-C(4)-C(5) 115.5(13)
C(4)-C(5)-H(5A) 109.5
C(4)-C(5)-H(5B) 109.5
H(5A)-C(5)-H(5B) 109.5
C(4)-C(5)-H(5C) 109.4
H(5A)-C(5)-H(5C) 109.5
H(5B)-C(5)-H(5C) 109.5
N(3)-C(6)-O(3) 137.1(13)
N(3)-C(6)-N(4) 114.9(11)
O(3)-C(6)-N(4) 108.0(11)
2. nitrile silicification reaction application
2- phenyl -2-（Three silyloxies）Propionitrile
The ml (3.3mmol) of 0.2mmol compound I, benzaldehyde 0.1mL, TMSCN 0.3,2mL absolute methanols, in succession Added under 30 ~ 35 C, after 48 hours, add water quenching and go out after post layer（Petroleum ether/dichloromethane：5/1）, obtain colorless oil Liquid, conversion ratio：18.0 %;1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31– 7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8 (x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。
3. Henle reaction application
0.0675g compounds（I）, be placed in 25mL flasks, sequentially add 1mL tetrahydrofurans, 0.3 mL nitromethanes and 0.5mmol ethyl pyruvates, stirring at normal temperature reaction 48h, separately sampled progress1HNMR is detected, and its conversion ratio is 86%;1 H NMR (CDCl 3 ): δ ) 4.86 (d,J =13.8 Hz, 1H), 4.58 (d, J =13.8 Hz, 1H), 4.34 (m, 2H), 3.85(s, 1H), 1.46 (s, 3H), 1.33 (t, J ) 7.2 Hz, 3H).13 C NMR (CDCl 3 ):δ= 173.4, 80.9, 72.4, 63.0, 23.8, 13.9。

Claims (4)

  1. A kind of 1. acetylurea dimer compound, it is characterized in that as the compound shown in below formula：
    （Ⅰ）.
  2. 2. as the acetylurea dimer crystalline compounds described in claim 1（I）, 273（2）At a temperature of k, in Oxford, X- is penetrated On line single crystal diffractometer, with the monoclinic system through graphite monochromator monochromatization, P21,Cell parameter：a = 7.012(3) Å α = 90°；b = 5.088(3) Å β = 98.208(10)°.；c = 13.674(7) Å γ = 90 °.
  3. 3. the acetylurea dimer crystalline compounds（I）Synthetic method, including synthesize, separate and purify, described synthesis is Under the conditions of anhydrous and oxygen-free, weigh acetylurea 1.0046g and a cyano group propenyl benzene 1.3275g is put into two mouthfuls of flasks of 100mL, add 20mL absolute methanols, which are stirred at room temperature, makes its dissolving；After reaction 48 hours, heat filtering, dichloromethane and absolute ethyl alcohol are added, and will Solution volatilizees naturally, obtains white crystal.
  4. 4. the purposes of the acetylurea dimer crystalline compounds (I) described in claim 1, is the nitrile as catalyst in benzaldehyde Applied in the Henle reaction of silication and ethyl pyruvate, its conversion ratio is respectively up to 18% and 86%.
CN201710975450.6A 2017-08-07 2017-10-19 A kind of synthetic method and purposes of acetylurea dimer crystalline compounds Pending CN107674004A (en)

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CN107652205A (en) * 2017-10-24 2018-02-02 合肥祥晨化工有限公司 A kind of synthetic method and purposes of imines crystalline compounds
CN107602414A (en) * 2017-10-29 2018-01-19 合肥祥晨化工有限公司 A kind of synthetic method and purposes of diphenyl-ketoxime dimer crystalline compounds
CN107698465B (en) * 2017-11-14 2019-07-05 合肥祥晨化工有限公司 A kind of synthetic method of acetylurea crystalline compounds
CN112480126B (en) * 2020-12-11 2022-03-11 合肥工业大学 Preparation and application of 5-alkyl quinazoline derivative

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M. G. VORONKOV等: "Acyl Iodides in Organic Synthesis.Reactions of Acetyl Iodide with Urea, Thiourea,and Their N,N′-Disubstituted Derivatives", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 *
曾柏清: "催化醛的不对称硅腈化反应研究", 《中国优秀硕士学位论文全文数据库》 *

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