CN110183352A - β-carbonyl-(alpha-cyano imines) class compound and its synthetic method - Google Patents
β-carbonyl-(alpha-cyano imines) class compound and its synthetic method Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- -1 methoxyl group Chemical group 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 125000004185 ester group Chemical group 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 239000002024 ethyl acetate extract Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- TZGIRWVSWPFWBP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxymethylbenzene Chemical compound CC(C)(C)OCC1=CC=CC=C1 TZGIRWVSWPFWBP-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- XLRMAHQDIAUVRV-UHFFFAOYSA-N C(#N)C1=C(C(C=CC1=O)=O)C#N.[Cl] Chemical compound C(#N)C1=C(C(C=CC1=O)=O)C#N.[Cl] XLRMAHQDIAUVRV-UHFFFAOYSA-N 0.000 claims 2
- 150000002527 isonitriles Chemical class 0.000 claims 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052709 silver Inorganic materials 0.000 abstract description 8
- 239000004332 silver Substances 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 11
- 150000008422 chlorobenzenes Chemical class 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 8
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 7
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RJFSDTDWWBECIL-UHFFFAOYSA-N trifluoro(methyl)-$l^{4}-sulfane Chemical compound CS(F)(F)F RJFSDTDWWBECIL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WHTVZRBIWZFKQO-AWEZNQCLSA-N (S)-chloroquine Chemical compound ClC1=CC=C2C(N[C@@H](C)CCCN(CC)CC)=CC=NC2=C1 WHTVZRBIWZFKQO-AWEZNQCLSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001264 acyl cyanides Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229960003677 chloroquine Drugs 0.000 description 2
- WHTVZRBIWZFKQO-UHFFFAOYSA-N chloroquine Natural products ClC1=CC=C2C(NC(C)CCCN(CC)CC)=CC=NC2=C1 WHTVZRBIWZFKQO-UHFFFAOYSA-N 0.000 description 2
- 238000000375 direct analysis in real time Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000012063 dual-affinity re-targeting Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 201000004792 malaria Diseases 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 2
- TXJPRCGTEFCCRB-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxy]ethylbenzene Chemical compound CC(C)(C)OC(C)C1=CC=CC=C1 TXJPRCGTEFCCRB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GUGDVZNGVZOFGA-UHFFFAOYSA-N 1-chloro-4-[(2-methylpropan-2-yl)oxymethyl]benzene Chemical class CC(C)(C)OCC1=CC=C(Cl)C=C1 GUGDVZNGVZOFGA-UHFFFAOYSA-N 0.000 description 1
- IMKLDAYQQGCIGZ-UHFFFAOYSA-N 1-methyl-2-[(2-methylpropan-2-yl)oxymethyl]benzene Chemical class CC1=CC=CC=C1COC(C)(C)C IMKLDAYQQGCIGZ-UHFFFAOYSA-N 0.000 description 1
- WIAUQNWVCMSYSG-UHFFFAOYSA-N 1-methyl-3-[(2-methylpropan-2-yl)oxymethyl]benzene Chemical class CC1=CC=CC(COC(C)(C)C)=C1 WIAUQNWVCMSYSG-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- NAAMXDTVYZTNQQ-UHFFFAOYSA-N 3,4-dichlorobenzene-1,2-dicarbonitrile Chemical class ClC1=CC=C(C#N)C(C#N)=C1Cl NAAMXDTVYZTNQQ-UHFFFAOYSA-N 0.000 description 1
- NPUKDXXFDDZOKR-UHFFFAOYSA-N 3-(1-phenylethyl)-4-imidazolecarboxylic acid ethyl ester Chemical compound CCOC(=O)C1=CN=CN1C(C)C1=CC=CC=C1 NPUKDXXFDDZOKR-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- NRYJLJPKWPCDNL-UHFFFAOYSA-N C(=O)=C(CC#N)C1=CC=CC=C1 Chemical compound C(=O)=C(CC#N)C1=CC=CC=C1 NRYJLJPKWPCDNL-UHFFFAOYSA-N 0.000 description 1
- CCWTZPVWTAGKAE-UHFFFAOYSA-N C(C)(C)(C)OC(C1=CC=CC=C1)Br Chemical compound C(C)(C)(C)OC(C1=CC=CC=C1)Br CCWTZPVWTAGKAE-UHFFFAOYSA-N 0.000 description 1
- GZBISCGOVVVNRN-UHFFFAOYSA-N C(C)(C)(C)OC(C1=CC=CC=C1)OC Chemical compound C(C)(C)(C)OC(C1=CC=CC=C1)OC GZBISCGOVVVNRN-UHFFFAOYSA-N 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- 241000223960 Plasmodium falciparum Species 0.000 description 1
- WDQPRBKCNORRAR-UHFFFAOYSA-N [Ag].CS(=O)(=O)O.[F] Chemical compound [Ag].CS(=O)(=O)O.[F] WDQPRBKCNORRAR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KLODEUGQIDVPQV-UHFFFAOYSA-N methyl 2-[(2-methylpropan-2-yl)oxy]-2-phenylacetate Chemical class COC(=O)C(OC(C)(C)C)c1ccccc1 KLODEUGQIDVPQV-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/61—Carboxylic acid nitriles containing cyano groups and nitrogen atoms being part of imino groups bound to the same carbon skeleton
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of β-carbonyl-(alpha-cyano imines) class compound and its synthetic method, the structural formulas of the compound are as follows:.Wherein: R1For hydrogen, methyl, methoxyl group, ester group, fluorine, chlorine, bromine, alkenyl or alkynyl (C2~C3)；R2For hydrogen, methyl；R3For hydrogen, methyl.β-carbonyl-(alpha-cyano imines) class compound of the invention is a kind of very valuable organic synthesis intermediate, carbonyl cyano imines skeleton has shown that the reactivity of multiplicity, therefore β-carbonyl-(alpha-cyano imines) class compound can be converted into other corresponding reactive compounds.The raw material that the method for the present invention uses is simple and easy to get, and the cyano sources using tert-butyl isonitrile as reaction have best reactivity and substrate adaptability under the promotion of fluoroform alkyl sulfonic acid silver.Conventional reaction dissolvent is used in reaction process, easy to operate, mild condition is environmental-friendly, and yield generally arrives outstanding, there is good development prospect in the industrial production.
Description
Technical field
The present invention relates to a kind of β-carbonyl-(alpha-cyano imines) class compound and its synthetic methods.
Background technique
β-carbonyl-(alpha-cyano imines) class compound is a kind of organic synthesis intermediate with application value, be can be used for
Rapid build structure other organic compounds more complicated and changeable.For example, Zhao et al. β-carbonyl-(alpha-cyano imines) class
A series of 2- cyano -3- aryl quinoxaline compounds of compound synthesis, referring to bibliography: Zhao, Y.-L.et
al.Org.Biomol.Chem.,2016,14,165.Zarranz et al. has synthesized a variety of 2- cyano -3- aryl quinoxalines
It closes object and tests its inhibitory activity to plasmodium falciparum bacterial strain FcB1, the results showed that all shown more there are four types of noval chemical compound
High inhibitory activity, referring to bibliography: Zarranz, B.et al.Arzneim.-Forsch. (Drug Res.), 2005,
55,754.Chloroquine is a kind of key agents of primary treatment malaria, and Vicente's et al. the study found that compare chloroquine, a variety of quinolines
Quinoline class compound has lower IC50With the higher selectivity to K1 bacterial strain, future is likely to become to anti-plasmodium falciparum,
The novel drugs for treating malaria, referring to bibliography: Vicente, E.et al.Eur.J.Med.Chem., 2008,43,1903.Separately
Outside, Kroehnke et al. has found, it is anti-that the hydrolysis of β-carbonyl-alpha-cyano imines skeleton is realized in certain density hydrochloric acid solution
It answers, obtains β-carbonyl-α-carboxylic acid compound, referring to bibliography: Kroehnke, F.et al.Eur.J.Inorg.Chem.,
1947,80,298).And in certain density sodium hydroxide solution, then β-carbonyl-Alpha-hydroxy imine compound can be obtained,
Referring to bibliography: Kroehnke, F.et al.Eur.J.Inorg.Chem., 1947,80,298.
It can be seen that β-carbonyl-alpha-cyano imine compound is a kind of and its important compound, scientist as a result,
β-carbonyl-alpha-cyano imine compound efficiently synthesized carried out more research and exploration.It was once reported in document
Synthesize β-carbonyl-alpha-cyano imine compound method mainly include the following types: (one) Kroehnke et al. with nitrone be original
Material is reacted with Cymag, has obtained a series of β-carbonyl-alpha-cyano imine compound, and wherein R is alkyl, aryl, furans
Base, thienyl etc..But it uses the Cymag of severe toxicity as cyano sources in reaction, has limited the purposes of reaction, see reference document:
Kroehnke,F.et al.Eur.J.Inorg.Chem.,1947,80,298。
(2) Laskar et al. is under the action of lithium bromide, passes through the anti-of 3- carbonyl -3- phenylpropanenitrile and nitroso aromatic hydrocarbons
It answers, has obtained β-carbonyl-alpha-cyano imine compound.But the raw material of reaction is more expensive, and substrate is more complicated, should not obtain
, being reacted by several steps can just obtain, and see reference document: Laskar, D.D.et al.Synth.Comm., and 2001,31,
1427。
(3) Zhao et al. alpha-amido nitrile compounds and TMSCN, DBU react, and have synthesized a series of β-carbonyl-(α-
Cyano imines) class compound.But for the type of the compound synthesized by the reaction than relatively limited, yield is lower, uses in reaction
TMSCN costly is as cyano sources, and see reference document: Zhao, Y.-L.et al.Org.Biomol.Chem., and 2016,
14,165。
In conclusion at present β-carbonyl-(alpha-cyano imines) class compound synthetic method mainly have it is above several, still
Than relatively limited, raw material substrate source is not easy, is more complicated the type for the compound product that the above method can synthesize, and often to lead to
It crosses several steps to react to obtain, preparing for raw material is more expensive；Or reaction condition is harsher, is not easy to promote, reaction cost is higher.
The method being currently known mostly is first building β-carbonyl-alpha-amido skeleton compound, for some with special substituent
Compound still needs to new cheap, the efficient synthetic method of development.
Summary of the invention
One of the objects of the present invention is to provide a kind of β-carbonyl-(alpha-cyano imines) class compounds.
The second object of the present invention is to provide the synthetic method of such compound.
In order to achieve the above objectives, the reaction mechanism that the method for the present invention uses are as follows:
Wherein, R1For the alkynyl of hydrogen, methyl, methoxyl group, ester group, fluorine, chlorine, bromine, the alkenyl of C2~C3 or C2~C3；
R2For hydrogen or methyl；
R3For hydrogen or methyl.
According to above-mentioned reaction mechanism, present invention employs the following technical solutions:
A kind of β-carbonyl-(alpha-cyano imines) class compound, it is characterised in that the structural formula of such compound are as follows:
Wherein: R1For hydrogen, methyl, methoxyl group, ester group, fluorine, chlorine, bromine, the alkenyl of C2~C3 or C2~C3 alkynyl；
R2For hydrogen or methyl；
R3For hydrogen or methyl.
A kind of synthetic method preparing above-mentioned β-carbonyl-(alpha-cyano imines) class compound, it is characterised in that this method
With following steps: under an inert atmosphere, by benzyl tertbutyl ether, tert-butyl isonitrile, silver trifluoromethanesulfonate, dichloro dicyanobenzenes
Quinone (DDQ) is by 1.0:(4.0~5.0): 0.1:(2.0~3.0) molar ratio be added in chloro benzene solvent, at 80~90 DEG C
It is stirred to react to reaction raw materials and disappears；It is cooled to room temperature, ethyl acetate extracts product, and saturated salt solution washs respectively, uses after dry
Rotary Evaporators remove solvent, obtain crude product；The crude product is through separating-purifying, β-carbonyl-(alpha-cyano imines) for being replaced
Class compound；The structural formula of the benzyl tertbutyl ether are as follows:The structure of the tert-butyl isonitrile
Formula are as follows:
β-carbonyl-(alpha-cyano imines) class compound of the invention is a kind of very valuable organic synthesis intermediate,
Carbonyl cyano imines skeleton has shown that the reactivity of multiplicity, therefore β-carbonyl-(alpha-cyano imines) class compound can convert
For other corresponding reactive compounds.
The raw material that the method for the present invention uses is simple and easy to get, the cyano sources using tert-butyl isonitrile as reaction, in fluoroform
Under the promotion of alkyl sulfonic acid silver, preferable reactivity and substrate adaptability are shown.Conventional reaction is made in reaction process
Solvent, easy to operate, mild condition is environmental-friendly, and yield generally arrives outstanding.Therefore, there is good development in the industrial production
Prospect.
Specific embodiment
Embodiment one: (E)-N- (tert-butyl) -2- oxo -2- phenylacetyl imido grpup cyanide
(E)-N- (tert-butyl) -2- oxo -2- phenylacetyl imido grpup cyanide uses following step: 1. at 1000 milliliters
4.93 grams of benzyl tertbutyl ethers of addition in reaction kettle, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of silver trifluoromethanesulfonate, 13.60 grams
2,3-Dichloro-5,6-dicyano-1,4-benzoquinone, 300 milliliters of chlorobenzenes, is heated to 80 DEG C.It is tracked and is reacted with thin-layer chromatography method,
It disappears to reaction raw materials；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, and saturated salt solution washs respectively, dry
Remove solvent with Rotary Evaporators afterwards, obtains crude product；3. crude product column chromatographs (petroleum ether: ethyl acetate=100:1) and purifies,
Obtain 5.3 grams of (E)-N- (tert-butyl) -2- oxo -2- phenylacetyl imido grpup cyanides, structural formula are as follows:Yield is 82%.Fusing point: 34-35 DEG C.
IR(KBr,cm-1):3737,2975,2929,2860,2221,1676,1457,1282,1230,915,729.
1H NMR(CDCl3, 500MHz): δ 8.05 (d, J=7.3Hz, 2H), 7.63 (t, J=7.3Hz, 1H), 7.48 (t, J
=7.8Hz, 2H), 1.55 (s, 9H)
13C NMR(CDCl3,125MHz):δ186.3,136.6,134.3,133.4,131.2,128.5,110.8,60.9,
29.1.
LC-MS(ESI)m/z:215.1[M+H].
HRMS(DART Positive)m/z:calcd for C13H15N2O[M+H]215.1179,found215.1178.
Embodiment two: (E)-N- (tert-butyl) -2- oxo -2- (p-methylphenyl) acetimidoyl cyanide
(E)-N- (tert-butyl) -2- oxo -2- (p-methylphenyl) acetimidoyl cyanide uses following step: 1. existing
5.35 grams are added in 1000 milliliters of reaction kettles to methylbenzyl tertbutyl ether, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of fluoroform
Sulfonic acid silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.Use thin layer
Analysis method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated common salt
Water washs respectively, removes solvent with Rotary Evaporators after drying, obtains crude product；3. crude product chromatographs (petroleum ether: acetic acid second with column
Ester=100:1) purifying, obtain 5.76 grams of (E)-N- (tert-butyl) -2- oxo -2- (p-methylphenyl) acetimidoyl cyanidings
Object, structural formula are as follows:Yield is 84%.Fusing point: 60-61 DEG C.
IR(KBr,cm-1):3679,2969,2361,1659,1551,1289,921,836,760.
1H NMR(CDCl3, 500MHz): δ 7.96 (d, J=8.2Hz, 2H), 7.27 (d, J=7.9Hz, 2H), 2.43 (s,
3H),1.55(s,9H).
13C NMR(CDCl3,125MHz):δ186.0,145.6,136.7,131.3,130.8,129.3,110.9,60.8,
29.1,22.0.
LC-MS(ESI)m/z:229.1[M+H].
HRMS(DART Positive)m/z:calcd for C14H17N2O[M+H]229.1335,found 229.1334.
Embodiment three: (E)-N- (tert-butyl) -2- (4- methoxyphenyl) -2- oxo acetimidoyl cyanide
(E)-N- (tert-butyl) -2- (4- methoxyphenyl) -2- oxo acetimidoyl cyanide uses following step:
1. 5.83 grams are added in 1000 milliliters of reaction kettles to methoxy-benzyl tertbutyl ether, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram
Silver trifluoromethanesulfonate, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.With
Thin-layer chromatography method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, satisfies
It is washed respectively with saline solution, removes solvent with Rotary Evaporators after drying, obtain crude product；3. crude product with column chromatograph (petroleum ether:
Ethyl acetate=100:1) purifying, 5.86 grams of (E)-N- (tert-butyl) -2- (4- methoxyphenyl) -2- oxo imido are obtained for second
Acyl cyanide, structural formula are as follows:Yield is 80%.Fusing point: 38-39 DEG C.
IR(KBr,cm-1):3743,2976,2221,2051,1661,1599,1263,1175,1113,917,843.
1H NMR(CDCl3, 500MHz): δ 8.10 (d, J=9.0Hz, 2H), 6.95 (d, J=9.0Hz, 2H), 3.89 (s,
3H),1.55(s,9H).
13C NMR(CDCl3,125MHz):δ184.5,164.6,136.7,133.6,126.0,113.9,110.8,60.5,
55.6,29.0.
EI-MS m/z:244.1[M+].
HRMS(EI)m/z:calcd for C14H16N2O2[M+]244.1212,found 244.1218.
Example IV: (E) -4- (2- (tertbutylimido) -2- Cyanoacetyl) methyl benzoate
(E) -4- (2- (tertbutylimido) -2- Cyanoacetyl) methyl benzoate uses following step: 1. 1000
6.67 grams of para Toluic Acid's carbomethoxy benzyl tertbutyl ethers of addition in milliliter reaction kettle, 17.00 milliliters of tert-butyl isonitriles, 0.78 gram three
Fluorine methanesulfonic acid silver, 20.43 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 90 DEG C.With thin
Layer chromatography method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturation
Saline solution washs respectively, removes solvent with Rotary Evaporators after drying, obtains crude product；3. crude product chromatographs (petroleum ether: second with column
Acetoacetic ester=100:1) purifying, 5.64 grams of (E) -4- (2- (tertbutylimido) -2- Cyanoacetyl) methyl benzoate is obtained,
Its structural formula are as follows:Yield is 69%.Fusing point: 65-66 DEG C.
IR(KBr,cm-1):3852,3740,2978,2219,1727,1683,1514,1281,1199,1108,918,
868,737.
1H NMR(CDCl3, 500MHz): δ 8.12 (d, J=8.6Hz, 2H), 8.08 (d, J=8.6Hz, 2H), 3.96 (s,
3H),1.55(s,9H).
13C NMR(CDCl3,125MHz):δ186.0,166.2,137.0,136.5,134.6,131.0,129.5,
110.5,61.2,52.7,29.1.
EI-MS m/z:272.1[M+].
HRMS(EI)m/z:calcd for C15H16N2O3[M+]272.1161,found 272.1166.
Embodiment five: (E)-N- (tert-butyl) -2- (4- fluorophenyl) -2- oxo acetimidoyl cyanide
(E)-N- (tert-butyl) -2- (4- fluorophenyl) -2- oxo acetimidoyl cyanide uses following step: 1. existing
5.47 grams are added in 1000 milliliters of reaction kettles to luorobenzyl tertbutyl ether, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of trifluoro methylsulphur
Sour silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.Use thin-layer chromatography
Method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated salt solution
It washs respectively, removes solvent with Rotary Evaporators after drying, obtain crude product；3. crude product chromatographs (petroleum ether: ethyl acetate with column
=100:1) purifying, 5.55 grams of (E)-N- (tert-butyl) -2- (4- fluorophenyl) -2- oxo acetimidoyl cyanides are obtained,
Its structural formula are as follows:Yield is 80%.Fusing point: 49-50 DEG C.
IR(KBr,cm-1):3739,2979,2931,2597,2211,1917,1678,1598,1294,1232,1114,
917,846,773.
1H NMR(CDCl3, 500MHz): δ 8.13 (m, 2H), 7.15 (t, J=8.6Hz, 2H), 1.55 (s, 9H)
19F NMR(CDCl3,470MHz):δ-102.5(m,Ar-F).
13C NMR(CDCl3,125MHz):δ184.7,167.5,165.5,136.6,134.1,134.0,129.8,
129.7,115.9,115.8,110.6,60.9,29.1.
EI-MS m/z:232[M+].
HRMS(EI)m/z:calcd for C13H13N2OF[M+]232.1012,found 232.1016.
Embodiment six: (E)-N- (tert-butyl) -2- (4- chlorphenyl) -2- oxo acetimidoyl cyanide
(E)-N- (tert-butyl) -2- (4- chlorphenyl) -2- oxo acetimidoyl cyanide uses following step: 1. existing
5.96 grams of p-chlorobenzyl tertbutyl ethers, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of trifluoro methylsulphur are added in 1000 milliliters of reaction kettles
Sour silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.Use thin-layer chromatography
Method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated salt solution
It washs respectively, removes solvent with Rotary Evaporators after drying, obtain crude product；3. crude product chromatographs (petroleum ether: ethyl acetate with column
=100:1) purifying, 5.98 grams of (E)-N- (tert-butyl) -2- (4- chlorphenyl) -2- oxo acetimidoyl cyanides are obtained,
Its structural formula are as follows:Yield is 80%.Fusing point: 89-90 DEG C.
IR(KBr,cm-1):3679,2971,2926,2360,1682,1585,1365,1291,1088,918,839,768.
1H NMR(CDCl3, 500MHz): δ 8.02 (d, J=8.8Hz, 2H), 7.45 (d, J=8.7Hz, 2H), 1.55 (s,
9H).
13C NMR(CDCl3,125MHz):δ185.1,141.0,136.5,132.5,131.8,128.9,110.6,61.0,
29.1.
EI-MS m/z:248.1[M+].
HRMS(EI)m/z:calcd for C13H13N2OCl[M+]248.0716,found 248.0719.
Embodiment seven: (E)-N- (tert-butyl) -2- (4- bromophenyl) -2- oxo acetimidoyl cyanide
(E)-N- (tert-butyl) -2- (4- bromophenyl) -2- oxo acetimidoyl cyanide uses following step: 1. existing
7.29 grams are added in 1000 milliliters of reaction kettles to bromobenzyl tertbutyl ether, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of trifluoro methylsulphur
Sour silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.Use thin-layer chromatography
Method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated salt solution
It washs respectively, removes solvent with Rotary Evaporators after drying, obtain crude product；3. crude product chromatographs (petroleum ether: ethyl acetate with column
=100:1) purifying, 6.24 grams of (E)-N- (tert-butyl) -2- (4- bromophenyl) -2- oxo acetimidoyl cyanides are obtained,
Its structural formula are as follows:Yield is 71%.Fusing point: 101-102 DEG C.
IR(KBr,cm-1):3445,3101,2977,2358,1680,1582,1472,1291,1067,917,868,839,
765.
1H NMR(CDCl3, 500MHz): δ 7.93 (d, J=8.4Hz, 2H), 7.61 (d, J=8.6Hz, 2H), 1.54 (s,
9H).
13C NMR(CDCl3,125MHz):δ185.3,136.5,132.6,132.2,131.9,129.9,110.5,61.1,
29.1.
LC-MS(ESI)m/z:295.0[M+H(81Br)],293.0[M+H(79Br)].
HRMS(ESI)m/z:calcd for C13H13N2OBr[M+H]293.0284,found 293.0283.
Embodiment eight: (E)-N- (tert-butyl) -2- oxo -2- (4- ((trimethyl silyl) acetenyl) phenyl) imido
For acetyl group cyanide
(E)-N- (tert-butyl) -2- oxo -2- (4- ((trimethyl silyl) acetenyl) phenyl) acetimidoyl
Cyanide uses following step: 7.81 grams being 1. added in 1000 milliliters of reaction kettles to (trimethylsilyl) acetenyl benzyl uncle
Butyl ether, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of silver trifluoromethanesulfonate, 13.60 grams of chloro- 5,6- dicyano-Isosorbide-5-Nitraes-of 2,3- bis-
Benzoquinones, 300 milliliters of chlorobenzenes, is heated to 80 DEG C.It is tracked and is reacted with thin-layer chromatography method, until reaction raw materials disappear；2. reaction knot
Shu Hou is cooled to room temperature.Ethyl acetate extracts product, and saturated salt solution washs respectively, removes solvent with Rotary Evaporators after drying,
Obtain crude product；3. crude product column chromatographs (petroleum ether: ethyl acetate=100:1) and purifies, 6.37 grams of (E)-N- (tertiary fourths are obtained
Base) -2- oxo -2- (4- ((trimethyl silyl) acetenyl) phenyl) acetimidoyl cyanide, structural formula are as follows:Yield is 68%.Fusing point: 70-71 DEG C.
IR(KBr,cm-1):3437,2971,2217,2156,1931,1673,1630,1598,1285,1244,1114,
864,765.
1H NMR(CDCl3, 500MHz): δ 7.99 (d, J=8.5Hz, 2H), 7.53 (d, J=8.5Hz, 2H), 1.54 (s,
9H),0.26(s,9H).
13C NMR(CDCl3,125MHz):δ185.5,136.5,132.8,131.9,130.9,129.2,110.6,
103.9,99.5,60.9,29.1,-0.1.
EI-MS m/z:301.1[M+].
HRMS(EI)m/z:calcd for C18H22N2OSi[M+]310.1501,found 310.1497.
Embodiment nine: (E) -3- (4- ((E) -2- (tertbutylimido) -2- Cyanoacetyl) phenyl) methyl acrylate
(E) -3- (4- ((E) -2- (tertbutylimido) -2- Cyanoacetyl) phenyl) methyl acrylate uses following step: 1. existing
7.45 grams of 4- methyl acrylate base benzyl tertbutyl ethers of addition in 1000 milliliters of reaction kettles, 13.60 milliliters of tert-butyl isonitriles, 0.78
Gram silver trifluoromethanesulfonate, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 90 DEG C.
It is tracked and is reacted with thin-layer chromatography method, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product,
Saturated salt solution washs respectively, removes solvent with Rotary Evaporators after drying, obtains crude product；3. crude product chromatographs (petroleum with column
Ether: ethyl acetate=100:1) purifying, 6.12 grams of (E)-N- (tert-butyl) -2- oxo -2- (o-tolyl) imido are obtained for second
Acyl cyanide, structural formula are as follows:Yield is 68%.Fusing point: 97-98 DEG C.
IR(KBr,cm-1):3846,3742,3413,2981,2218,1934,1718,1654,1605,1301,1200,
915,836,771.
1H NMR(CDCl3, 500MHz): δ 8.07 (d, J=8.0Hz, 2H), 7.70 (d, J=16.0Hz, 1H), 7.60 (d,
J=8.2Hz, 2H), 6.54 (d, J=16.0Hz, 1H), 3.82 (s, 3H), 1.55 (s, 9H)
13C NMR(CDCl3,125MHz):δ185.5,166.9,143.1,139.7,136.6,134.5,131.7,
127.9,121.2,110.6,61.0,52.1,29.1.
EI-MS m/z:298.1[M+].
HRMS(EI)m/z:calcd for C17H18N2O3[M+H]298.1317,found 298.1311.
Embodiment ten: (E)-N- (tert-butyl) -2- oxo -2- (o-tolyl) acetimidoyl cyanide
(E)-N- (tert-butyl) -2- oxo -2- (o-tolyl) acetimidoyl cyanide uses following step: 1. existing
5.35 grams of 2- methylbenzyl tertbutyl ethers, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of fluoroform are added in 1000 milliliters of reaction kettles
Sulfonic acid silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 90 DEG C.Use thin layer
Analysis method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated common salt
Water washs respectively, removes solvent with Rotary Evaporators after drying, obtains crude product；3. crude product chromatographs (petroleum ether: acetic acid second with column
Ester=100:1) purifying, obtain 5.77 grams of (E)-N- (tert-butyl) -2- oxo -2- (o-tolyl) acetimidoyl cyanidings
Object, structural formula are as follows:Yield is 84%.Fusing point: 56-57 DEG C.
IR(KBr,cm-1):3696,2979,2208,1679,1603,1271,1204,915,749.
1H NMR(CDCl3, 500MHz): δ 7.51 (d, J=7.7Hz, 1H), 7.43 (t, J=7.4Hz, 1H), 7.28-
7.23(m,2H),2.46(s,3H),1.49(s,9H).
13C NMR(CDCl3,125MHz):δ189.9,139.8,137.6,133.5,132.5,131.8,131.5,
125.2,110.8,60.7,29.1,21.2.
LC-MS(ESI)m/z:229.1[M+H].
HRMS(ESI)m/z:calcd for C14H17N2O[M+H]229.1335,found 229.1334.
Embodiment 11: (E)-N- (tert-butyl) -2- oxo -2- (tolyl) acetimidoyl cyanide
(E)-N- (tert-butyl) -2- oxo -2- (tolyl) acetimidoyl cyanide uses following step: 1. existing
5.35 grams of 3- methylbenzyl tertbutyl ethers, 13.60 milliliters of tert-butyl isonitriles, 0.78 gram of fluoroform are added in 1000 milliliters of reaction kettles
Sulfonic acid silver, 13.60 grams of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinones, 300 milliliters of chlorobenzenes are heated to 80 DEG C.Use thin layer
Analysis method tracking reaction, until reaction raw materials disappear；2. after reaction, being cooled to room temperature.Ethyl acetate extracts product, saturated common salt
Water washs respectively, removes solvent with Rotary Evaporators after drying, obtains crude product；3. crude product chromatographs (petroleum ether: acetic acid second with column
Ester=100:1) purifying, obtain 5.72 grams of (E)-N- (tert-butyl) -2- oxo -2- (tolyl) acetimidoyl cyanidings
Object, structural formula are as follows:Yield is 83%.
IR(KBr,cm-1):2977,2217,1674,1594,1290,1231,946,795,754.
1H NMR(CDCl3, 500MHz): δ 7.85-7.82 (m, 2H), 7.44 (d, J=8.5Hz, 1H), 7.35 (t, J=
7.6Hz,1H),2.41(s,3H),1.55(s,9H).
13C NMR(CDCl3,125MHz):δ186.4,138.3,136.4,135.0,133.3,131.3,128.4,
128.2,110.7,60.7,29.0,21.4.
EI-MS m/z:228[M+].
HRMS(EI)m/z:calcd for C14H16N2O[M+]228.1263,found 228.1265.
Claims (2)
1. a kind of β-carbonyl-(alpha-cyano imines) class compound, it is characterised in that the structural formula of such compound are as follows:
Wherein: R1For hydrogen, methyl, methoxyl group, ester group, fluorine, chlorine, bromine, the alkenyl of C2~C3 or C2~C3 alkynyl；
R2For hydrogen or methyl；
R3For hydrogen or methyl.
2. a kind of synthetic method for preparing β-carbonyl-according to claim 1 (alpha-cyano imines) class compound, feature
It is that this method has following steps: under an inert atmosphere, by benzyl tertbutyl ether, tert-butyl isonitrile, silver trifluoromethanesulfonate, two
Chlorine dicyano benzoquinone (DDQ) is by 1.0:(4.0~5.0): 0.1:(2.0~3.0) molar ratio be added in chloro benzene solvent, in
It is stirred to react at 80~90 DEG C to reaction raw materials and is disappeared；It is cooled to room temperature, ethyl acetate extracts product, and saturated salt solution is washed respectively
It washs, removes solvent with Rotary Evaporators after drying, obtain crude product；The crude product is through separating-purifying, β-carbonyl-for being replaced
(alpha-cyano imines) class compound；The structural formula of the benzyl tertbutyl ether are as follows:The tertiary fourth
The structural formula of base isonitrile are as follows:
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