CN106083505A - A kind of method synthesizing β iodo nitroolefin compounds - Google Patents
A kind of method synthesizing β iodo nitroolefin compounds Download PDFInfo
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- SRVHYDWPPHAZCM-VQHVLOKHSA-N CC1C=CC(/C(/C)=C/N=O)=CC1 Chemical compound CC1C=CC(/C(/C)=C/N=O)=CC1 SRVHYDWPPHAZCM-VQHVLOKHSA-N 0.000 description 1
- OCIZEZIMGPBKLD-UHFFFAOYSA-N CCOC(CC(c1ccccc1)=O)c1ccc(C)cc1 Chemical compound CCOC(CC(c1ccccc1)=O)c1ccc(C)cc1 OCIZEZIMGPBKLD-UHFFFAOYSA-N 0.000 description 1
- POUJNYLSTVIQAV-VURMDHGXSA-N [O-][N+](/C=C(/c1ccccc1)\I)=O Chemical compound [O-][N+](/C=C(/c1ccccc1)\I)=O POUJNYLSTVIQAV-VURMDHGXSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
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- 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
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
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- C07B2200/07—Optical isomers
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Abstract
The invention provides the synthetic method of the β iodo nitroolefin compound shown in a kind of formula (III): the nitrous acid special butyl ester shown in the replacement alkynes shown in formula (I), propiodal, formula (II) is mixed in solvent reaction completely and obtains reactant liquor, after reacting 4～6h at 25～80 DEG C, reactant liquor is post-treated obtains described β iodo nitroolefin compounds；Described solvent is oxolane, acetonitrile, acetone or 1,2 dichloroethanes；Replacement alkynes shown in described formula (I), propiodal are 1:0.5～1:2～5 with the ratio of the amount of the material that feeds intake of the nitrous acid special butyl ester shown in formula (II)；Inventive substrate adaptability is good, reaction condition is gentle, is not related to the use of oxidant and metallic catalyst, safety and environmental protection, and operation is simple, is more conducive to its application in medicine synthesizes.
Description
(1) technical field
The present invention relates to a kind of method synthesizing β-iodo nitroolefin, special with acetylene hydrocarbon compound, propiodal and nitrous acid
Butyl ester is raw material, can realize the synthesis of multiple β-iodo nitroolefin in a mild condition.
(2) background technology
β-iodo nitroolefin is the reaction intermediate that a class is important in organic synthesis, it is possible to occur multiple conversion to obtain
To different important chemical.Such as, under palladium chtalyst, easily there is cross-coupling reaction in the halogen iodine contained in its structure；Knot
The nitro contained in structure can be converted into amino under catalytic reduction system, thus is further converted to the various organic of other
Thing.But up to the present, the synthetic method about this compounds is reported the fewest.Document is had to report Sornsiri, H.；
Natthapol,S.；Tassaporn,S.；Manat,P.；Vichai,R.；Darunee,S.；Thaworn,J.；Chutima,
K.；Eur.J.Org.Chem., 2014,33,7,433 7442., make oxidant, nitrous with ammonium persulfate-sodium bisulfate (Oxone)
Acid sodium (NaNO2) it is nitro source, potassium iodide is to obtain corresponding β-iodo nitroolefin compound under halogen source, but
It is that the use of strong oxidizer Oxone makes some that the group of its sensitivity not be suitable for such reaction.In view of with present on ask
Topic, designs an anaerobic agent and participates in, and the new method without the synthesis β-iodo nitroolefin compound of metal catalytic seems very
Necessary.
(3) summary of the invention
Object of the present invention is to provide the new method of a kind of β-iodo nitroolefin compou nd synthesis.
The technical solution used in the present invention is as follows:
A kind of synthetic method of the β-iodo nitroolefin compound shown in formula (III), described synthetic method is:
Acetylene hydrocarbon compound shown in formula (I) and the nitrous acid special butyl ester shown in propiodal, formula (II) are mixed in solvent logical
Crossing TLC tracking reaction and obtain reactant liquor completely, after reacting 4h at 50 DEG C, reactant liquor is post-treated obtains described β-iodo nitre
Base olefin(e) compound；Described solvent is oxolane, acetonitrile, acetone or 1,2-dichloroethanes；
The material that feeds intake of the acetylene hydrocarbon compound shown in described formula (I) and the nitrous acid special butyl ester shown in propiodal, formula (II)
The ratio of amount is 1:0.5～1:2～5；
In formula (I):
R1For substituted-phenyl, pyridine radicals or thienyl, described substituted-phenyl is by halogen, C1～5Alkyl or C1～5Alkoxyl takes
The phenyl in generation；R2For H or phenyl.
Synthetic method of the present invention, the replacement alkynes shown in the most described formula (I) is selected from one of following: phenylacetylene,
3-chlorobenzene acetylene, 3-fluorobenzene acetylene, 4-chlorobenzene acetylene or 4-methylbenzene acetylene.
Replacement alkynes shown in formula of the present invention (I) is selected from one of following: phenylacetylene, 3-chlorobenzene acetylene or 3-fluorophenethyl
Alkynes.
Further, the propiodal described in the most described synthetic method is elemental iodine.
Further, described solvent is preferably oxolane, it is recommended that the volumetric usage of described solvent is with formula (I) institute
The amount replacing alkynes material shown is calculated as 2ml/0.5mmol～6ml/0.5mmol.
The substitutedphenylethynyl shown in formula (I) described in further, the propiodal shown in formula (II), the Asia shown in formula (III)
The ratio of the amount of the material that feeds intake of nitric acid spy's butyl ester is 1:0.5:2.
Preferable reaction temperature is 25～80 DEG C, and the response time is 4～6h.
The method recommending described reactant liquor post processing is: after reaction terminates, first carry out reactant liquor being concentrated under reduced pressure to give oil
Shape thing, gained grease carries out column chromatography for separation again, with the petrol ether/ethyl acetate mixed liquor of volume ratio 20:1 or 9:1 for washing
De-agent, collects the eluent containing target compound, is dried, obtains described β-iodo nitroolefin compound after solvent is evaporated off.
Concrete, it is recommended that the synthetic method of described β-iodo nitroolefin compound is:
Replacement acetylene hydrocarbon compound shown in formula (I) is mixed in solvent with the nitrous acid special butyl ester shown in propiodal, formula (II)
In at 25～80 DEG C react 4～6h, first carry out reactant liquor being concentrated under reduced pressure to give grease, gained grease carried out post again
Chromatography, with the petrol ether/ethyl acetate mixed liquor of volume ratio 20:1 or 9:1 as eluant, collects and merges containing targeted
The eluent of compound, is dried after solvent is evaporated off, obtains described β-iodo nitroolefin compounds；
Replacement acetylene hydrocarbon compound shown in described formula (I) and the thing that feeds intake of the nitrous acid special butyl ester shown in propiodal, formula (II)
The ratio of the amount of matter is 1:0.5～1:2～5；Replacement acetylene hydrocarbon compound shown in described formula (I) is selected from one of following: phenylacetylene, 3-
Chlorobenzene acetylene, 3-fluorobenzene acetylene, 4-chlorobenzene acetylene or 4-methylbenzene acetylene；In described formula, propiodal is elemental iodine；Described solvent
Selected from one of following: oxolane, acetonitrile, acetone or 1,2-dichloroethanes, the volumetric usage of described solvent is with formula (I) Suo Shi
Replace alkynes material amount be calculated as 2ml/0.5mmol～6ml/0.5mmol.
Compared with prior art, the invention has the beneficial effects as follows:
(1) safety and environmental protection, does not produce waste gas, is more conducive to its application in medicine synthesizes；
(2) compared with prior art, yield is improved, and reaction condition is gentle, it is not necessary to add strong oxidizer, and substrate adapts to
Property is good, and multiple substituent group can realize corresponding β-iodo nitroolefin compounds；
(3) directly with replacement acetylene hydrocarbon compound as raw material, whole process need not catalyst, and operation is simple, is one
Plant the variation route of synthesis β-iodo nitroolefin compound containing various different substituents.
(4) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but protection scope of the present invention not only
It is limited to this.
Embodiment 1
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitro
Vinyl) benzene (compound 1) 111.3mg, yield 80.9%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；1H NMR(500MHz,CDCl3)δ7.63(s,1H),7.34–7.26(m,3H),
7.25–7.19(m,2H).13C NMR(125MHz,CDCl3)δ142.18,137.44,127.56,127.52,126.25,
112.77.
Embodiment 2
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (127mg, 0.5mmol) and nitrous acid special butyl ester (103.1mg,
1mmol) it is mixed in 2ml tetrahydrofuran solvent and joins in flask, react 4 hours at 50 DEG C.After TLC detection reaction terminates,
With column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitroethylene base) benzene
(compound 1) 112.4mg, yield 81.7%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, rf value 0.26, with the rf value of the compound 1 that embodiment 1 obtains
Identical.
Embodiment 3
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(257.8mg, 2.5mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitre
Base vinyl) benzene (compound 1) 108.7mg, yield 79.1%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value phase
With.
Embodiment 4
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 25 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitro
Vinyl) benzene (compound 1) 89.9mg, yield 65.4%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value phase
With.
Embodiment 5
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 80 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitro
Vinyl) benzene (compound 1) 105.1mg, yield 76.4%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value phase
With.
Embodiment 6
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 6 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitre
Base vinyl) benzene (compound 1) 107.3mg, yield 78.47%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value phase
With.
Embodiment 7
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml acetonitrile solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection reaction knot
Shu Hou, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitroethylene
Base) benzene (compound 1) 106.4mg, yield 77.4%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value phase
With.
Embodiment 8
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml acetone solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection reaction knot
Shu Hou, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitroethylene
Base) benzene (compound 1) 90.0mg, yield 65.5%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Being detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value is identical
Embodiment 9
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml 1, and 2-dichloroethane solvent joins in flask, reacts 4 hours at 50 DEG C.TLC examines
After measured reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (the iodo-2-of 1-
Nitroethylene base) benzene (compound 1) 101.4mg, yield 73.8%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Being detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value is identical
Embodiment 10
Compound 1
By phenylacetylene (51mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 6ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (1-iodo-2-nitro
Vinyl) benzene (compound 1) 71.9mg, yield 52.3%, E/Z, > 99:1.
Characterization of The Products: weak yellow liquid；Being detected by TLC, with the contrast of the compound 1 that embodiment 1 obtains, rf value is identical
Embodiment 11
Compound 2
By 3-fluorobenzene acetylene (60.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-fluoro-3-(1-
Iodo-2-nitroethylene base) benzene (compound 2) 115.6mg, yield 78.9%, E/Z, 93:7.
Characterization of The Products: yellow semisolid；1H NMR(500MHz,CDCl3)δ7.72(s,1H),7.37(m,1H),7.09–
7.04(m,2H),7.04–7.00(m,1H).13C NMR (125MHz, CDCl3) δ 162.15 (d, J=247.5Hz), 143.57,
140.36 (d, J=8.3Hz), 130.35 (d, J=8.4Hz), 122.80,117.18 (d, J=21.25Hz), 114.49 (d, J
=21.25Hz), 111.17 (d, J=2.3Hz).
Embodiment 12
Compound 3
By 3-chlorobenzene acetylene (68.3mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-chloro-3-(1-
Iodo-2-nitroethylene base) benzene (compound 3) 130.5mg, yield 84.3%, E/Z, 97:3.
Characterization of The Products: faint yellow solid, mp 54-57 DEG C；1H NMR(500MHz,CDCl3)δ7.73(s,1H),7.36–
7.33 (m, 2H), 7.30 (dd, J=2.2,1.4Hz, 1H), 7.20 7.15 (m, 1H).13C NMR(125MHz,CDCl3)δ
143.64, 140.15,134.50,130.26,129.90,127.17,125.19,111.17.
Embodiment 13
Compound 4
By 3-bromobenzene acetylene (90.5mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-bromo-3-(1-
Iodo-2-nitroethylene base) benzene (compound 4) 135.4mg, yield 78.4%, E/Z, 97:3.
Characterization of The Products: faint yellow solid, mp 56-57 DEG C；1H NMR(500MHz,CDCl3)δ7.73(s,1H),7.50(m,
1H), 7.45 (t, J=1.7Hz, 1H), 7.28 7.25 (m, 2H), 7.24 7.21 (m, 1H).13C NMR(125MHz,CDCl3)δ
143.63,140.36,133.16,130.09,129.93,125.65,122.39,111.05.
Embodiment 14
Compound 5
By 2-chlorobenzene acetylene (68.3mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-chloro-2-(1-
Iodo-2-nitroethylene base) benzene (compound 5) 138.6mg, yield 78.3%, E/Z, 97:3.
Characterization of The Products: weak yellow liquid；1H NMR(500MHz,CDCl3) δ 7.79 (s, 1H), 7.40 (dd, J=7.2,
2.1Hz, 1H), 7.29 (pd, J=7.5,1.8Hz, 2H), 7.20 (dd, J=6.9,2.5Hz, 1H).13C NMR(125MHz,
CDCl3)δ144.89,137.44,130.77,130.32,129.86,127.69,127.09,109.54.
Embodiment 15
Compound 6
By 2-methylbenzene acetylene (58.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-methyl-2-
(1-iodo-2-nitroethylene base) benzene (compound 6) 68.2mg, yield 45.8%, E/Z, 96:4.
Characterization of The Products: weak yellow liquid；1H NMR(500MHz,CDCl3)δ7.80(s,1H),7.28–7.22(m,3H),
7.12–7.05(m,1H),2.24(s,3H).13C NMR(125MHz,CDCl3)δ144.11,138.26,133.80,130.55,
129.80,126.19,125.91,113.91,19.40.
Embodiment 16
Compound 7
By 4-methylbenzene acetylene (58.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-methyl-4-
(1-iodo-2-nitroethylene base) benzene (compound 7) 115.4mg, yield 79.9%, E/Z, 97:3.
Characterization of The Products: faint yellow solid, mp55-57 DEG C；1H NMR(500MHz,CDCl3)δ7.65(s,1H),7.18–
7.10(m,4H),2.31(s,3H).13C NMR(125MHz,CDCl3)δ142.58,140.85,135.51,129.24,
127.52,114.52,21.47.
Embodiment 17
Compound 8
By 4-fluorobenzene acetylene (60.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) the fluoro-4-of isolated (Z)-1-
(1-iodo-2-nitroethylene base) benzene (compound 8) 103.7mg, yield 70.8%.Characterization of The Products: faint yellow solid, mp 50-51
℃；1H NMR(500MHz,CDCl3)δ7.67(s,1H),7.28–7.23(m,2H),7.05–6.99(m,2H).13C NMR
(125MHz,CDCl3) δ 163.44 (d, J=251.25Hz), 143.24,134.42 (d, J=3.75Hz), 129.70 (d, J=
8.75Hz), 129.67,115.849 (d, J=22.5Hz).
Embodiment 18
Compound 9
By 4-chlorobenzene acetylene (68.3mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-chloro-4-(1-
Iodo-2-nitroethylene base) benzene (compound 9) 122.3mg, yield 79.0%, E/Z, 94:6.
Characterization of The Products: yellow solid, mp 90-91 DEG C；1H NMR(500MHz,CDCl3)δ7.73(s,1H),7.39–7.35
(m,2H),7.28–7.23(m,2H).13C NMR(125MHz,CDCl3)δ143.34,136.88,136.36,130.30,
129.19,128.89,128.73,112.11.
Embodiment 19
Compound 10
By 4-bromobenzene acetylene (90.5mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-bromo-4-(1-
Iodo-2-nitroethylene base) benzene (compound 10) 141.9mg, yield 76.5%, E/Z, 83:17.
Characterization of The Products: yellow solid, mp95-96 DEG C；1H NMR(500MHz,CDCl3)δ7.72(s,1H),7.53–7.49
(m,2H),7.20–7.15(m,2H).13C NMR(125MHz,CDCl3)δ143.25,137.32,132.12,131.76,
130.43,128.91,124.57,112.11.
Embodiment 20
Compound 11
4-Methoxy-phenylacetylene (66.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid is special
Butyl ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC examines
After measured reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-methoxy
Base-4-(1-iodo-2-nitroethylene base) benzene (compound 11) 60mg, yield 39.3%, E/Z, 98:2.
Characterization of The Products: yellow liquid；1H NMR(500MHz,CDCl3)δ7.71(s,1H),7.33–7.29(m,2H),
6.91–6.86(m,2H),3.84(s,3H).13C NMR(125MHz,CDCl3)δ161.21,142.04,130.23,129.91,
114.82,113.89,55.44.
Embodiment 21
Compound 12
By 4-amylbenzene acetylene (86.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-amyl group-4-
(1-iodo-2-nitroethylene base) benzene (compound 12) 116.9mg, yield 67.7%, E/Z, 95:5.
Characterization of The Products: yellow liquid；1H NMR(500MHz,CDCl3)δ7.70(s,1H),7.27–7.21(m,2H),
7.18 (d, J=8.3Hz, 2H), 2.63 2.58 (m, 2H), 1.65 1.58 (m, 2H), 1.36 1.30 (m, 4H), 0.90 (t, J
=7.0Hz, 3H).13C NMR(125MHz,CDCl3)δ145.79,142.49,135.52,128.49, 127.59,114.58,
35.78,31.47,30.71,22.48,13.99.
Embodiment 22
Compound 13
By 4-propylbenzene acetylene (72.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-propyl group-4-
(1-iodo-2-nitroethylene base) benzene (compound 13) 123.7mg, yield 78.0%, E/Z, 97:3.
Characterization of The Products: yellow liquid；1H NMR(500MHz,CDCl3)δ7.71(s,1H),7.26–7.22(m,2H),7.18
(d, J=8.3Hz, 2H), 2.63 2.58 (m, 2H), 1.69 1.61 (m, 2H), 0.95 (t, J=7.3Hz, 3H).13C NMR
(125MHz,CDCl3)δ145.53,142.52,135.59,128.58,127.57,114.56,37.86,24.14,13.82.
Embodiment 23
Compound 14
4-amyl phenyl ether acetylene (94.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid is special
Butyl ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC examines
After measured reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated 1-penta oxygen
Base-4-(1-iodo-2-nitroethylene base) benzene (compound 14) 32.4mg, yield 18.7%, E/Z, 98:2.
Characterization of The Products: yellow liquid；1H NMR(500MHz,CDCl3)δ7.70(s,1H), 7.32–7.27(m,2H),
6.88 6.84 (m, 2H), 3.98 (t, J=6.5Hz, 2H), 1.82 1.76 (m, 2H), 1.47 1.41 (m, 2H), 1.41 1.34
(m, 2H), 0.93 (t, J=7.2Hz, 3H).13C NMR(125MHz,CDCl3)δ160.88,141.88,129.96,129.89,
115.07,114.30,68.21,28.80,28.13,22.41,14.00.
Embodiment 24
Compound 15
4-nitrobenzene acetylene (36.8mg, 0.25mmol), iodine (31.8mg, 0.125mmol) and nitrous acid is special
Butyl ester (51.6mg, 0.5mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC examines
After measured reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (Z)-1-nitre
Base-4-(1-iodo-2-nitroethylene base) benzene (compound 15) 29.3mg, yield 45.8%.
Characterization of The Products: yellow solid, mp114-116 DEG C；1H NMR(500MHz,CDCl3)δ8.30–8.25(m,2H),
7.79(s,1H),7.49–7.44(m,2H).13C NMR(125MHz,CDCl3)δ148.30,144.98,144.34,129.92,
128.03,124.05,123.92,109.77.
Embodiment 25
Compound 16
By 3,5-bis-trifluoromethyl phenylacetylene (119.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and Asia
Nitric acid spy's butyl ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 little at 50 DEG C
Time.After TLC detection reaction terminates, by column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated
(Z)-3,5-bis-trifluoromethyl-4-(1-iodo-2-nitroethylene base) benzene (compound 16) 103.1mg, yield 65.2%.
Characterization of The Products: faint yellow solid, mp 95-97 DEG C；1H NMR(500MHz,CDCl3)δ7.90(s,1H),7.85(s,
1H),7.75(s,2H).13C NMR(125MHz,CDCl3) δ 144.85,140.76,132.28 (m, J=33.75Hz),
127.26,123.76 (t, J=3.54Hz), 121.62-119.45 (d, J=271.25Hz), 108.51 (s).
Embodiment 26
Compound 17
By tolan (89.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid special butyl ester
(103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detection is anti-
After should terminating, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (Z)-(iodo-2-of 1-
Nitroethylene-1,2-diphenyl) hexichol (compound 17) 82.8mg, yield 47.2%.
Characterization of The Products: faint yellow solid, mp 101-102 DEG C；1H NMR(500MHz,CDCl3)δ7.67–7.60(m,2H),
7.53–7.47(m,3H),7.46–7.41(m,2H),7.41–7.31(m,3H).13C NMR(125MHz,CDCl3)δ154.28,
139.60,134.38,130.72,129.83,129.31,128.87,128.73,127.63,102.67.
Embodiment 27
Compound 18
By 2-thiophene acetylene (54.1mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 20:1) isolated (Z)-2-(1-
Iodo-2-nitroethylene base) thiophene (compound 18) 42.5mg, yield 30.2%.
Characterization of The Products: brown solid, mp 82-85 DEG C；1H NMR(500MHz,CDCl3)δ7.90(s,1H),7.64
(ddd, J=6.1,4.5,1.0Hz, 2H), 7.20 (dd, J=5.1,3.9Hz, 1H).13C NMR(125MHz,CDCl3)δ
141.72,139.97,134.31,131.24,128.49,100.20.
Embodiment 28
Compound 19
By 3-ethynyl pyridine (51.5mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 9:1) isolated (Z)-3-(1-
Iodo-2-nitroethylene base) pyridine (compound 19) 56.1mg, yield 40.7%.
Characterization of The Products: yellow solid, mp 121-122 DEG C；1H NMR(500MHz,CDCl3) δ 8.65 (ddd, J=4.8,
1.6,1.0Hz, 1H), 7.80 7.69 (m, 2H), 7.39 (dt, J=7.9,1.0Hz, 1H), 7.32 7.25 (m, 1H).13C NMR
(125 MHz,CDCl3)δ155.39,149.65,144.04,136.80,124.32,122.43,112.44.
Embodiment 29
Compound 20
By 2-ethynyl pyridine (51.5mg, 0.5mmol), iodine (63.5mg, 0.25mmol) and nitrous acid spy's fourth
Ester (103.1mg, 1mmol) is mixed in 2ml tetrahydrofuran solvent and joins in flask, reacts 4 hours at 50 DEG C.TLC detects
After reaction terminates, with column chromatography chromatogram method (eluent: petrol ether/ethyl acetate volume ratio 9:1) isolated 2-(the iodo-2-of 1-
Nitroethylene base) pyridine (compound 20) 53.6mg, yield 38.8%, E/Z, 99:1.
Characterization of The Products: brown solid, mp 95-96 DEG C；1H NMR(500MHz,CDCl3)δ8.68–8.54(m,2H),7.83
(s, 1H), 7.64 (ddd, J=7.9,2.2,1.8Hz, 1H), 7.36 (ddd, J=8.0,4.9,0.7Hz, 1H).13C NMR
(125MHz,CDCl3)δ150.80,147.46,144.20,135.02,134.91,123.11,109.49。
Claims (10)
1. the synthetic method of the β shown in a formula (III)-iodo nitroolefin compounds, it is characterised in that described synthesis
Method is:
It is mixed in the nitrous acid special butyl ester shown in the replacement alkynes shown in formula (I), propiodal, formula (II) in solvent to react and obtains completely
To reactant liquor, reactant liquor is post-treated obtains described β-iodo nitroolefin compounds；Described solvent be oxolane,
Acetonitrile, acetone or 1,2-dichloroethanes；
The ratio of the amount of the material that feeds intake of the replacement alkynes shown in described formula (I), propiodal and the nitrous acid special butyl ester shown in formula (II)
For 1:0.5～1:2～5；
In formula (I):
R1For substituted-phenyl, pyridine radicals or thienyl, described substituted-phenyl is by halogen, C1～5Alkyl or C1～5Alkoxyl is substituted
Phenyl；R2For H or phenyl.
2. synthetic method as claimed in claim 1, it is characterised in that the replacement alkynes shown in described formula (I) is one of following:
Phenylacetylene, 3-chlorobenzene acetylene, 3-fluorobenzene acetylene, 4-chlorobenzene acetylene or 4-methylbenzene acetylene.
3. synthetic method as claimed in claim 2, it is characterised in that the replacement alkynes shown in described formula (I) selected from following it
One: phenylacetylene, 3-chlorobenzene acetylene or 3-fluorobenzene acetylene.
4. synthetic method as claimed in claim 1, it is characterised in that the propiodal described in described synthetic method is elemental iodine.
5. synthetic method as claimed in claim 1, it is characterised in that the solvent described in described synthetic method is oxolane.
6. synthetic method as claimed in claim 1, it is characterised in that the volumetric usage of the solvent described in described synthetic method
It is calculated as 2ml/0.5mmol～6ml/0.5mmol with the amount replacing alkynes material shown in formula (I).
7. synthetic method as claimed in claim 1, it is characterised in that the substitutedphenylethynyl shown in described formula (I), formula (II) institute
The ratio of the amount of the material that feeds intake of the nitrous acid special butyl ester shown in the propiodal that shows, formula (III) is 1:0.5:2.
8. synthetic method as claimed in claim 1, it is characterised in that reaction react under the conditions of temperature is 25～80 DEG C 4～
6h。
9. the synthetic method as described in one of claim 1～8, it is characterised in that the method for described reactant liquor post processing is: anti-
After should terminating, reactant liquor first carries out being concentrated under reduced pressure to give grease, and described grease carries out column chromatography for separation again, with volume ratio
The petrol ether/ethyl acetate mixed liquor of 20:1 or 9:1 is eluant, collects the eluent merged containing target compound, is evaporated off molten
It is dried after agent, obtains described β-iodo nitroolefin compounds.
10. synthetic method as claimed in claim 8, it is characterised in that described method is carried out as follows: by formula (I) institute
The replacement acetylene hydrocarbon compound, the propiodal that show are mixed in solvent at 25～80 DEG C reaction with the nitrous acid special butyl ester shown in formula (II)
4～6h, reactant liquor first carries out being concentrated under reduced pressure to give grease, and described grease carries out column chromatography for separation again, with volume ratio 20:1
Or the petrol ether/ethyl acetate mixed liquor of 9:1 is eluant, collect the eluent merged containing target compound, after solvent is evaporated off
It is dried, obtains described β-iodo nitroolefin compounds；Replacement acetylene hydrocarbon compound shown in described formula (I) and propiodal, formula
(II) ratio of the amount of the material that feeds intake of the nitrous acid special butyl ester shown in is 1:0.5～1:2～5；Replacement alkynes shown in described formula (I)
Hydrocarbon compound is selected from one of following: phenylacetylene, 3-chlorobenzene acetylene, 3-fluorobenzene acetylene, 4-chlorobenzene acetylene or 4-methylbenzene acetylene；
In described formula, propiodal is elemental iodine；Described solvent is selected from one of following: oxolane, acetonitrile, acetone or 1,2-dichloroethanes,
The volumetric usage of described solvent is calculated as 2ml/0.5mmol～6ml/ with the amount replacing alkynes material shown in formula (I)
0.5mmol。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382821A (en) * | 2016-07-07 | 2017-11-24 | 浙江工业大学 | Synthesis method of beta-iodine-N-alkoxy amine compound |
| CN107501024A (en) * | 2017-09-15 | 2017-12-22 | 安徽省应用技术研究院 | A kind of synthetic method of 1,2 2 iodo alkenes compounds |
| CN113943199A (en) * | 2021-10-18 | 2022-01-18 | 浙江工业大学 | Method for synthesizing amide compound by taking nitrile and diarylmethane as raw materials |
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2016
- 2016-07-07 CN CN201610546493.8A patent/CN106083505A/en active Pending
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| MEHMAN S. YUSUBOV,ET AL.: ""A Facile Synthesis of α -Iodo- β -nitroalkenes from Alkynes Using I2/NO3- or KI/NO3-"", 《SYNTHETIC COMMUNICATIONS》 * |
| UTTAM DUTTA,ET AL.: ""Aerobic Oxynitration of Alkynes with tBuONO and TEMPO"", 《ORGANIC LETTERS》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382821A (en) * | 2016-07-07 | 2017-11-24 | 浙江工业大学 | Synthesis method of beta-iodine-N-alkoxy amine compound |
| CN107382821B (en) * | 2016-07-07 | 2020-02-21 | 浙江工业大学 | Synthesis method of β -iodine-N-alkoxy amine compound |
| CN107501024A (en) * | 2017-09-15 | 2017-12-22 | 安徽省应用技术研究院 | A kind of synthetic method of 1,2 2 iodo alkenes compounds |
| CN113943199A (en) * | 2021-10-18 | 2022-01-18 | 浙江工业大学 | Method for synthesizing amide compound by taking nitrile and diarylmethane as raw materials |
| CN113943199B (en) * | 2021-10-18 | 2023-09-22 | 浙江工业大学 | Method for synthesizing amide compound by using nitrile and diaryl methane as raw materials |
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