CN109280025A - O-(N- ethyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof - Google Patents

O-(N- ethyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof Download PDF

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CN109280025A
CN109280025A CN201811154777.8A CN201811154777A CN109280025A CN 109280025 A CN109280025 A CN 109280025A CN 201811154777 A CN201811154777 A CN 201811154777A CN 109280025 A CN109280025 A CN 109280025A
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mmol
ethyl
pyrrolidinyl
dicarbapentaborane
nmr
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韩紫薇
章建民
杨戬
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/416—2,5-Pyrrolidine-diones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The present invention relates to a kind of novelO‑(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives preparation method.The structural formula of the compound are as follows:Wherein, R1Are as follows: phenyl, substituted-phenyl, benzyl, thienyl；R2Are as follows: phenyl, C1‑C3Alkyl, benzyl.This method is utilized for the first time under the catalysis of copper acetate, and ketoxime and N-ethylomaleimide one pot reaction have simultaneously obtained a series of newO‑(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives.For this method without in addition addition alkali, the yield of reaction is good, this novelO‑(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives have potential application in fields such as pesticide, medicine and new materials.

Description

O-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and its preparation Method
Technical field
The present invention relates to one kindO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof.
Technical background
Nitrogenous compound has the characteristics such as bioactivity is high, Environmental compatibility is good, in answering for medicine, pesticide and life science There is advantageous advantage in, be always the research emphasis of organic synthesis field.Oxime ether is a kind of common nitrogenous chemical combination Object has excellent bioactivity, suffers from and is widely applied on medicine and pesticide, and such as antitumor, antiviral, desinsection kills The bioactivity such as bacterium, anti-inflammatory.In the initiative of novel pesticide, oxime ether structure is still the effective active group being often selected, mostly Oxime ether has many advantages, such as efficient, low toxicity, low-residual, and therefore, oximido ether compound is obtained as a kind of pesticide activity Wide research and application.With the development and the promotion of biology drug resistance etc. of human society, more new oxime ethers are needed Molecule and preparation method thereof meets increasing need, so, more new oxime ether molecules of exploitation and preparation method thereof Research is an important job in current organic synthesis field, has important application value.
Oxime ether is usually prepared with the methods of Michael's addition or Williamson's condensation reaction.Such as Org. Lett., Method ketoxime described in 2007,9,2767-2770 and halogenated aryl hydrocarbon are catalyzed using CuI, Cs2CO3Make alkali, sodium tartrate makees chela Mixture, 1,10- ferrosin make ligand, are coupled to obtain the reaction of oxime ether；Synth. Commun., 2009, 39, 1857– 1863 use Triton B to participate in reacting as nonmetallic organic base, obtain the oxime ether of high yield；Synthesis. 2008, 2055-2064 synthesize beta-hydroxy oxime ether by a kind of high non-cubic method for selective synthesis in region；Synthesis., 2010, 1724-1730 utilize Ph3P/CCl4Flow back in acetonitrile catalysis ketoxime and alcohol of/DBU/TBAI catalyst system carries out reacting generation oxime Ether.
The synthesis of oxime ether usually requires the participation of alkali, and the less report of oxime ether synthetic method of alkali is not added, and not yet send out Now synthesized using ketoxime with N-ethylomaleimide is raw materialO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one The method of oxime ether derivatives；Have either with or without discovery and utilizes Cu (OAc)2 ·H2The copper compounds such as O are catalyzed ketoxime phase is prepared The report for the oxime ether derivatives answered.
Summary of the invention
One of the objects of the present invention is to provide one kindO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether spreads out Biology.
The second object of the present invention is to provide the preparation method of the derivative.This method is with ketoximes derivatives and N- ethyl Maleimide is raw material, and heating is reacted and obtained under the catalysis of the catalyst such as a water acetic acid copperO-(NEthyl -2,5- Dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives method.
In order to achieve the above objectives, reaction equation of the invention are as follows:
。
According to above-mentioned reactive mode, the present invention adopts the following technical scheme:
It is a kind ofO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives, it is characterised in that the structural formula of the derivative Are as follows:
In formula:
R1Are as follows: phenyl, substituted-phenyl, benzyl or thienyl；
R2Are as follows: phenyl, C1-C3Alkyl or benzyl.
It is a kind of prepare it is above-mentionedO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives method, feature It is the specific steps of this method are as follows: compound 1 and compound 2 and transition-metal catalyst are pressed into (1.5 ~ 1.75): 1:(0.15 ~ 0.2) molar ratio is dissolved in organic solvent, is reacted 8 ~ 10 hours at 75 ~ 90 DEG C；It is cooled and separated and obtains after purificationO- (NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives；The structural formula of the compound 1 are as follows:；Institute The structural formula for the compound 2 stated are as follows:。
Above-mentioned transition-metal catalyst are as follows: Cu (OAc)2 ·H2O 、Cu、Cu(OAc)2, CuCl or CuI.
Above-mentioned organic solvent is o-dichlorohenzene, toluene, dimethyl sulfoxide or N,N-dimethylformamide.
This method is utilized for the first time under the catalysis of copper acetate, and ketoxime and N-ethylomaleimide one pot reaction are simultaneously A series of new is obtainedO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives.This method is without in addition addition The yield of alkali, reaction is good, this novelO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives pesticide, The fields such as medicine and new material have application value.
Specific embodiment
The synthetic method and performance parameter of 30 embodiments are as follows:
Embodiment one: (E)-acetophenone oxime 0.1418g (1.05 mmol), N-ethylomaleimide are added in test tube 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) after test tube is carried out nitrogen displacement, are added 2mL o-dichlorohenzene, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NTwo carbonyl of ethyl -2,5- Base pyrrolidinyl) -1- phenyl -1- acetophenone oxime ether.White solid, yield: 78%, 83.1-83.6 DEG C of fusing point.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.57 – 7.53 (m, 2H), 7.37 – 7.31 (m, 3H), 5.11 (dd, J = 8.2, 4.1 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.3 Hz, 1H), 2.96 (dd, J = 18.4, 4.0 Hz, 1H), 2.28 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 175.00, 174.65, 157.92, 135.68, 129.83, 128.53, 126.30, 76.08, 35.41, 33.95, 13.09.
UV-vis (CH3CN) λmax/nm 251；
FT-IR ν/cm-1 (KBr): 3742, 3469, 3061, 2985, 2943, 1708, 1568, 1494, 1448, 1350, 1222, 1119, 1033, 882, 769, 693;
MALDI-FTICR MS m/z Calcd for C14H17O3N2 [M+H]+ 261.1234, Found 261.1231。
Embodiment two: addition (E) -3- methoxyacetophenone oxime 0.1722g (1.05 mmol), N- ethyl are suitable in test tube Butylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(3- methoxyphenyl) -1- acetophenone oxime ether.Yellow oil, yield: 85%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.23 (t, J = 8.0 Hz, 1H), 7.11 (dt, J = 7.7, 1.3 Hz, 1H), 7.08 (dd, J = 2.6, 1.6 Hz, 1H), 6.89 (ddd, J = 8.2, 2.6, 1.0 Hz, 1H), 5.09 (dd, J = 8.3, 4.0 Hz, 1H), 3.77 (s, 3H), 3.60 (q, J = 7.2 Hz, 2H), 3.02 (dd, J = 18.3, 8.3 Hz, 1H), 2.93 (dd, J = 18.3, 4.0 Hz, 1H), 2.24 (s, 3H), 1.18 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.84, 174.50, 159.53, 157.62, 136.91, 129.40, 118.73, 115.37, 111.58, 75.98, 55.23, 35.29, 33.77, 13.02, 12.98.
UV-vis (CH3CN) λmax/nm 253；
FT-IR ν/cm-1 (KBr): 3741, 3318, 3072, 2974, 2937, 1710, 1577, 1445, 1407, 1342, 1230, 1126, 1045, 869, 790, 690;
MALDI-FTICR MS m/z Calcd for C15H19O4N2 [M+H]+ 291.1339, Found 291.1337。
Embodiment three: addition (E) -4- methoxyacetophenone oxime 0.1722g (1.05 mmol), N- ethyl are suitable in test tube Butylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- methoxyphenyl) -1- acetophenone oxime ether.White solid, yield: 86%, fusing point 66.7-67.2℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.53 – 7.48 (m, 2H), 6.88 – 6.83 (m, 2H), 5.08 (dd, J = 8.1, 4.1 Hz, 1H), 3.81 (s, 3H), 3.63 (q, J = 7.2 Hz, 2H), 3.03 (dd, J = 18.4, 8.1 Hz, 1H), 2.96 (dd, J = 18.3, 4.2 Hz, 1H), 2.25 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 175.02, 174.63, 160.84, 157.26, 128.05, 127.57, 113.76, 75.84, 55.32, 35.28, 33.79, 12.99, 12.80.
UV-vis (CH3CN) λmax/nm 265；
FT-IR ν/cm-1 (KBr): 3742, 3468, 3064, 2980, 2945, 1705, 1599, 1450, 1405, 1346, 1251, 1114, 1028, 880, 808, 689;
MALDI-FTICR MS m/z Calcd for C15H19O4N2 [M+H]+ 291.1339, Found 291.1336。
Example IV: (E) -2- methyl acetophenone oxime 0.1575g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(2- aminomethyl phenyl) -1- acetophenone oxime ether.Yellow oil, yield: 84%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.29 – 7.19 (m, 4H), 5.11 (dd, J = 8.4, 4.2 Hz,1H), 3.60 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.3, 8.4 Hz,1H), 2.95 (dd, J = 18.3, 4.2 Hz,1H), 2.32 (s, 3H), 2.26 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.91, 174.33, 160.04, 136.35, 135.77, 130.84, 128.80, 128.12, 125.80, 75.78, 35.24, 33.81, 20.43, 16.60, 12.93.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr): 3740, 3345, 3066, 2975, 1710, 1447, 1403, 1346, 1231, 1087, 1048, 880, 762, 689;
MALDI-FTICR MS m/z Calcd for C15H19O3N2 [M+H]+ 275.1390, Found 275.1389。
Embodiment five: (E) -4- methyl acetophenone oxime 0.1575g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- aminomethyl phenyl) -1- acetophenone oxime ether.White solid, yield: 86%, fusing point 69.6- 69.9℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.46 – 7.42 (m, 2H), 7.14 (d, J = 7.9 Hz, 2H), 5.09 (dd, J = 8.2, 4.1 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.04 (dd,J = 18.3, 8.2 Hz, 1H), 2.96 (dd, J = 18.3, 4.1 Hz, 1H), 2.35 (s, 3H), 2.26 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.96, 174.59, 157.71, 139.84, 132.76, 129.10, 126.09, 75.89, 35.29, 33.80, 21.28, 12.98, 12.90.
UV-vis (CH3CN) λmax/nm 254；
FT-IR ν/cm-1 (KBr):3471, 3031, 2985, 1710, 1608, 1447, 1399, 1346, 1218, 1110, 1033, 877, 785, 687;
MALDI-FTICR MS m/z Calcd for C15H19O3N2 [M+H]+ 275.1390, Found 275.1388。
Embodiment six: (E) -4-hydroxyacetophenone oxime 0.1585g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- hydroxy phenyl) -1- acetophenone oxime ether.White solid, yield: 53%, fusing point 139.7- 140.1℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.45 – 7.37 (m, 2H), 6.81 – 6.71 (m, 2H), 5.59 (s, 1H), 5.10 (dd, J = 8.1, 4.1 Hz, 1H), 3.64 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.2 Hz, 1H), 2.97 (dd, J = 18.4, 4.2 Hz, 1H), 2.22 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 175.83, 175.09, 165.26, 157.49, 127.72, 115.34, 75.76, 35.21, 33.95, 12.97, 12.79.
UV-vis (CH3CN) λmax/nm 253；
FT-IR ν/cm-1 (KBr):3741, 3650, 3408, 3059, 2990, 2944, 1699, 1614, 1507, 1452, 1411, 1353, 1223, 1122, 1039, 880, 793, 696;
MALDI-FTICR MS m/z Calcd for C14H17O4N2 [M+H]+ 277.1183, Found 277.1181。
Embodiment seven: (E) -2- fluorophenethyl ketoxime 0.1607g (1.05 mmol), N- ethyl maleic are added in test tube Test tube is carried out nitrogen displacement by imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) Afterwards, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl- 2,5- dicarbapentaborane pyrrolidinyl) -1-(2- fluorophenyl) -1- acetophenone oxime ether.White solid, yield: 15%, fusing point 59.3-59.6 ℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.42 – 7.29 (m, 2H), 7.16 – 7.02 (m, 2H), 5.12 (dd, J = 8.4, 4.1 Hz, 1H), 3.61 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.4 Hz, 1H), 2.94 (dd, J = 18.3, 4.1 Hz, 1H), 2.29 (d, J = 2.6 Hz, 3H), 1.18 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.66, 174.34, 160.50 (d, J FC=252.0 Hz), 156.45 (d, J FC=2.5 Hz), 131.12 (d, J FC=7.6 Hz), 129.55 (q, J FC=3.8 Hz), 124.36 (d, J FC=11.3 Hz), 124.08 (d, J FC=3.8 Hz), 116.25 (d, J FC=22.7 Hz), 76.03, 35.24, 33.84, 15.68 (d, J FC=5.0 Hz), 12.90.
19F NMR (471 MHz, CDCl3) δ -113.97.
UV-vis (CH3CN) λmax/nm 237；
FT-IR ν/cm-1 (KBr):3742, 3474, 3070, 2990, 2941, 1717, 1608, 1490, 1448, 1408, 1349, 1220, 1123, 1034, 887, 772, 688;
MALDI-FTICR MS m/z Calcd for C14H16O3N2F [M+H]+ 279.1139, Found 279.1138。
Embodiment eight: (E) -3- fluorophenethyl ketoxime 0.1607g (1.05 mmol), N- ethyl maleic are added in test tube Test tube is carried out nitrogen displacement by imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) Afterwards, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl- 2,5- dicarbapentaborane pyrrolidinyl) -1-(3- fluorophenyl) -1- acetophenone oxime ether.Grease, yield: 74%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.37 – 7.22 (m, 2H), 7.11 – 7.03 (m, 0H), 5.12 (dd, J = 8.4, 4.0 Hz, 0H), 3.63 (q, J = 7.2 Hz, 1H), 3.06 (dd, J = 18.4, 8.4 Hz, 0H), 2.94 (dd, J = 18.4, 4.0 Hz, 0H), 2.26 (s, 1H), 1.21 (t, J = 7.2 Hz, 1H).
13C NMR (126 MHz, CDCl3) δ 174.65, 174.31, 162.71 (d, J = 246.0 Hz), 156.69 (d, J = 2.7 Hz), 137.68 (d, J = 7.5 Hz), 129.95 (d, J = 8.2 Hz), 121.87 (d, J = 3.0 Hz), 116.63 (d, J = 21.4 Hz), 113.11 (d, J = 23.2 Hz), 76.11, 35.26, 33.86, 12.96, 12.89.
19F NMR (471 MHz, CDCl3) δ -112.68.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3740, 3484, 3075, 2983, 2944, 1712, 1610, 1578, 1444, 1405, 1348, 1279, 1231, 1127, 1034, 874, 792, 689;
MALDI-FTICR MS m/z Calcd for C14H16O3N2F [M+H]+ 279.1139, Found 279.1138。
Embodiment nine: (E) -4- fluorophenethyl ketoxime 0.1607g (1.05 mmol), N- ethyl maleic are added in test tube Test tube is carried out nitrogen displacement by imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) Afterwards, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl- 2,5- dicarbapentaborane pyrrolidinyl) -1-(4- fluorophenyl) -1- acetophenone oxime ether.White solid, yield: 74%, fusing point 63.9-64.5 ℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.61 – 7.47 (m, 2H), 7.10 – 6.95 (m, 2H), 5.11 (dd, J = 8.3, 4.0 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.3, 8.3 Hz, 1H), 2.95 (dd, J = 18.4, 4.0 Hz, 1H), 2.26 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.81, 174.44, 164.68, 162.69(J=250.1 Hz), 156.79, 131.68, 131.66(J=3.8 Hz), 128.11, 128.04(J=8.35 Hz), 115.52, 115.35(J =21.5 Hz), 75.98, 35.25, 33.83, 12.96.
19F NMR (471 MHz, CDCl3) δ -111.19.
UV-vis (CH3CN) λmax/nm 251；
FT-IR ν/cm-1 (KBr):3741, 3478, 3070, 2971, 2942, 1708, 1602, 1512, 1453, 1409, 1347, 1229, 1114, 1037, 892, 786, 690;
MALDI-FTICR MS m/z Calcd for C14H16O3N2F [M+H]+ 279.1139, Found 279.1137。
Embodiment ten: addition (E) -2,3- difluoro acetophenone oxime 0.1796g (1.05 mmol), N- ethyl are suitable in test tube Butylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(2,3- difluorophenyl) -1- acetophenone oxime ether.White solid, yield: 71%, fusing point 86.4-86.8℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.18 (dtd, J = 9.7, 8.0, 1.8 Hz, 1H), 7.13 (ddt, J = 7.9, 6.1, 1.7 Hz, 1H), 7.04 (tdd, J = 8.0, 4.8, 1.6 Hz, 1H), 5.13 (dd, J = 8.4, 4.1 Hz, 1H), 3.61 (q, J = 7.2 Hz, 2H), 3.06 (dd, J = 18.4, 8.4 Hz, 1H), 2.93 (dd, J = 18.4, 4.1 Hz, 1H), 2.30 (d, J = 2.5 Hz, 3H), 1.18 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.49, 174.18, 155.38 (dd, J FC = 3.1, 1.8 Hz), 151.89 (d, J FC = 12.8 Hz), 147.79 (d, J FC = 13.8 Hz), 126.43 (d, J FC = 8.8 Hz), 124.12 (dd, J FC = 3.6, 1.9 Hz), 123.99 (dd, J FC = 7.0, 4.7 Hz), 118.16 (d, J FC = 17.3 Hz), 76.15, 35.19, 33.88, 15.54 (d, J FC = 4.6 Hz), 12.90.
19F NMR (471 MHz, CDCl3) δ -137.50, -139.66.
UV-vis (CH3CN) λmax/nm 243；
FT-IR ν/cm-1 (KBr):3750, 3473, 3080, 2976, 1707, 1618, 1579, 1473, 1411, 1343, 1267, 1223, 1123, 1041, 873, 808, 688;
MALDI-FTICR MS m/z Calcd for C14H15O3N2F2 [M+H]+ 297.1045, Found 297.1042。
Embodiment 11: (E) -2,4 difluorobenzene acetophenone oxime 0.1796g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(2,4- difluorophenyl) -1- acetophenone oxime ether.White solid, yield: 73%, fusing point 83.8-84.5℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.36 (td, J = 8.6, 6.5 Hz, 1H), 6.88 – 6.79 (m, 2H), 5.11 (dd, J = 8.4, 4.1 Hz, 1H), 3.61 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.4 Hz, 1H), 2.92 (dd, J = 18.3, 4.1 Hz, 1H), 2.27 (d, J = 2.6 Hz, 3H), 1.18 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.59, 174.24, 163.61 (dd, J FC = 251.9, 12.0 Hz), 160.81 (dd, J = 254.0, 12.0 Hz), 155.60 (d, J = 2.2 Hz), 130.61 (dd, J FC= 9.7, 4.8 Hz), 120.69 (dd, J FC = 12.3, 4.0 Hz), 111.51 (dd, J FC = 21.5, 3.6 Hz), 104.61 (t, J FC = 25.7 Hz), 76.06, 35.20, 33.85, 15.58 (d, J FC = 5.0 Hz), 12.90.
19F NMR (471 MHz, CDCl3) δ -107.72, -109.65.
UV-vis (CH3CN) λmax/nm 245；
FT-IR ν/cm-1 (KBr):3780, 3476, 3086, 2992, 2957, 1707, 1612, 1504, 1451, 1413, 1347, 1274, 1227, 1114, 1037, 853, 790, 691;
MALDI-FTICR MS m/z Calcd for C14H15O3N2F2 [M+H]+ 297.1045, Found 297.1042。
Embodiment 12: (E) -2,5- difluoro acetophenone oxime 0.1796g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(2,5- difluorophenyl) -1- acetophenone oxime ether.Yellow oil, yield: 42%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.11 (ddt, J = 6.9, 5.7, 1.8 Hz, 1H), 7.06 (td, J = 6.0, 1.8 Hz, 2H), 5.15 (dd, J = 8.4, 4.1 Hz, 1H), 3.65 (q, J = 7.1 Hz, 2H), 3.09 (dd, J = 18.4, 8.4 Hz, 1H), 2.95 (dd, J = 18.4, 4.1 Hz, 1H), 2.31 (d, J = 2.8 Hz, 3H), 1.22 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.46, 174.14, 159.24 (d, J FC = 2.3 Hz), 157.40 (d, J FC = 25.2 Hz), 155.49 (dd, J FC = 12.7, 2.4 Hz), 125.39 (dd, J FC = 14.6, 7.9 Hz), 117.60 (dd, J FC = 10.2, 8.6 Hz), 117.40 (dd, J FC = 11.0, 8.7 Hz), 115.78 (dd, J FC = 25.4, 3.8 Hz), 76.17, 35.17, 33.85, 15.36 (d, J FC = 5.7 Hz), 12.87.
19F NMR (471 MHz, CDCl3) δ -118.66, -119.89.
UV-vis (CH3CN) λmax/nm 241；
FT-IR ν/cm-1 (KBr):3741, 3479, 3078, 2984, 2943, 1712, 1586, 1491, 1411, 1347, 1283, 1234, 1186, 1126, 1033, 880, 772, 690;
MALDI-FTICR MS m/z Calcd for C14H15O3N2F2 [M+H]+ 297.1045, Found 297.1043。
Embodiment 13: (E) -3,4- difluoro acetophenone oxime 0.1796g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(3,4- difluorophenyl) -1- acetophenone oxime ether.Yellow oil, yield: 70%, fusing point 67.2-67.9℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.40 (ddd, J = 11.6, 7.7, 2.2 Hz, 1H), 7.29 (ddt, J = 8.4, 4.0, 1.6 Hz, 1H), 7.17 – 7.10 (m, 1H), 5.12 (dd, J = 8.4, 4.0 Hz, 1H), 3.64 (q, J = 7.2 Hz, 2H), 3.06 (dd, J = 18.4, 8.4 Hz, 1H), 2.96 – 2.89 (m, 1H), 2.25 (d, J = 0.9 Hz, 3H), 1.21 (td, J = 7.2, 1.0 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.58, 174.24, 155.81 (t, J FC = 1.9 Hz), 151.75 (dd, J FC = 138.4, 12.8 Hz), 149.76 (dd, J FC = 134.9, 13.0 Hz), 132.50 (d, J FC = 5.9 Hz), 122.48 (dd, J FC = 6.5, 3.6 Hz), 117.24 (d, J FC = 17.8 Hz), 115.22 (d, J FC= 18.8 Hz), 76.14, 35.20, 33.86, 12.95, 12.76.
19F NMR (471 MHz, CDCl3) δ -135.62, -137.00.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3468, 3076, 2998, 2945, 1714, 1519, 1412, 1348, 1324, 1273, 1227, 1105, 1036, 879, 773, 690;
MALDI-FTICR MS m/z Calcd for C14H15O3N2F2 [M+H]+ 297.1045, Found 297.1042。
Embodiment 14: (E) -3,5- difluoro acetophenone oxime 0.1796g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(3,5- difluorophenyl) -1- acetophenone oxime ether.White solid, yield: 81%, fusing point 87.8-88.6℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.08 (ddt, J = 9.0, 3.3, 1.7 Hz, 2H), 6.81 (tt, J = 8.6, 2.0 Hz, 1H), 5.13 (dd, J = 8.5, 4.0 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.07 (dd, J = 18.4, 8.5 Hz, 1H), 2.91 (dd, J = 18.4, 4.0 Hz, 1H), 2.24 (s, 2H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.43, 174.12, 163.89 (d, J FC = 12.6 Hz), 161.92 (d, J FC = 12.8 Hz), 155.75 (t, J FC = 3.2 Hz), 138.63 (t, J FC = 9.6 Hz), 109.26 (d, J FC = 6.7 Hz), 109.10 (d, J FC = 6.4 Hz), 104.99 (t, J FC = 25.4 Hz), 76.26, 35.21, 33.90, 12.95, 12.76.
19F NMR (471 MHz, CDCl3) δ -109.19.
UV-vis (CH3CN) λmax/nm 253；
FT-IR ν/cm-1 (KBr):3742, 3482, 3078, 2986, 2946, 1713, 1617, 1580, 1437, 1397, 1344, 1218, 1121, 1031, 862, 788, 689;
MALDI-FTICR MS m/z Calcd for C14H15O3N2F2 [M+H]+ 297.1045, Found 297.1042。
Embodiment 15: (E) -3,4,5- trifluoroacetophenone oxime 0.1974g (1.05 mmol), N- second are added in test tube Base maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), test tube is carried out After nitrogen displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO- (NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(3,4,5- trifluorophenyl) -1- acetophenone oxime ether.White solid, yield: 81%, 85.1-85.7 DEG C of fusing point.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.24 – 7.15 (m, 2H), 5.13 (dd, J = 8.5, 4.0 Hz, 1H), 3.63 (q, J = 7.3 Hz, 2H), 3.07 (dd, J = 18.4, 8.5 Hz, 1H), 2.90 (dd, J = 18.4, 4.0 Hz, 1H), 2.23 (s, 3H), 1.21 (t, J = 7.2 Hz,3H).
13C NMR (126 MHz, CDCl3) δ 174.37, 174.04, 154.93 (q, J FC = 2.6 Hz), 151.11 (ddd, J FC = 250.3, 10.2, 4.0 Hz), 140.63 (dt, J FC = 255.2, 15.2 Hz), 131.45 (td, J FC = 7.7, 4.7 Hz), 110.43 (dd, J FC = 17.3, 5.6 Hz), 76.30, 35.17, 33.90, 12.95, 12.58.
19F NMR (471 MHz, CDCl3) δ -133.55, -158.05.
UV-vis (CH3CN) λmax/nm 253；
FT-IR ν/cm-1 (KBr):3749, 3478, 3086, 2997, 2950, 1713, 1591, 1529, 1415, 1353, 1224, 1104, 1042, 872, 773, 693;
MALDI-FTICR MS m/z Calcd for C14H14O3N2F3 [M+H]+ 315.0948, Found 315.0951。
Embodiment 16: (E) -4-(trifluoromethyl is added in test tube) acetophenone oxime 0.2132g (1.05 mmol), N- Ethylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), by test tube into After the displacement of row nitrogen, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- trifluoromethyl) -1- acetophenone oxime ether.White solid, yield: 78%, 60.5-61.0 DEG C of fusing point.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.66 (dd, J = 8.9, 0.9 Hz, 1H), 7.59 (dd, J = 8.9, 0.8 Hz, 1H), 5.14 (dd, J = 8.5, 3.9 Hz, 0H), 3.62 (q, J = 7.2 Hz, 1H), 3.06 (dd, J = 18.4, 8.4 Hz, 1H), 2.93 (dd, J = 18.3, 4.0 Hz, 1H), 2.29 (s, 2H), 1.19 (t, J = 7.2 Hz, 2H).
13C NMR (126 MHz, CDCl3) δ 174.57, 174.24, 156.64, 138.88(q, J FC=1.26 Hz), 131.55(q, J FC=32.8 Hz), 126.49,125.37(q, J FC=3.8 Hz), 123.87(q, J FC=272.2 Hz), 76.20, 35.21, 33.84, 12.93, 12.89.
UV-vis (CH3CN) λmax/nm 255；
FT-IR ν/cm-1 (KBr):3740, 3477, 3066, 2953, 1708, 1613, 1569, 1455, 1410, 1327, 1224, 1111, 1051, 893, 803, 686;
MALDI-FTICR MS m/z Calcd for C15H16O3N2F3 [M+H]+ 329.1108, Found 329.1105。
Embodiment 17: (E) -2- chloro-acetophenone oxime 0.1775g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(2- chlorphenyl) -1- acetophenone oxime ether.Yellow oil, yield: 74%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.41 – 7.37 (m, 2H), 7.33 – 7.22 (m, 2H), 5.13 (dd, J = 8.3, 4.1 Hz, 1H), 3.59 (q, J = 7.2 Hz, 2H), 3.06 (dd, J = 18.3, 8.4 Hz, 1H), 2.95 (dd, J = 18.3, 4.1 Hz, 1H), 2.28 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.56, 174.27, 159.13, 135.94, 132.42, 130.21, 130.09, 130.04, 126.78, 76.01, 35.31, 33.85, 16.69, 12.90.
UV-vis (CH3CN) λmax/nm 251；
FT-IR ν/cm-1 (KBr):3740, 3483, 3063, 2981, 2939, 1711, 1603, 1533, 1441, 1405, 1347,1229, 1125, 1085, 1037, 887, 761, 692;
MALDI-FTICR MS m/z Calcd for C14H16O3N2Cl [M+H]+ 295.0844, Found 295.0842。
Embodiment 18: (E) -3- chloro-acetophenone oxime 0.1775g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(3- chlorphenyl) -1- acetophenone oxime ether.Yellow oil, yield: 53%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.54 (t, J = 1.9 Hz, 1H), 7.42 (dt, J = 7.7, 1.5 Hz, 1H), 7.33 (ddd, J = 8.0, 2.1, 1.1 Hz, 1H), 7.27 (t, J = 7.8 Hz, 1H), 5.12 (dd, J = 8.4, 4.0 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.4 Hz, 1H), 2.93 (dd, J = 18.3, 4.0 Hz, 1H), 2.25 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.65, 174.31, 156.56, 137.25, 134.49, 129.69, 129.67, 126.29, 124.29, 76.13, 35.27, 33.86, 12.98, 12.85.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3741, 3478, 3070, 2981, 2940, 1711, 1563, 1447, 1407, 1346, 1230, 1125, 1083, 1037, 897, 790, 694;
MALDI-FTICR MS m/z Calcd for C14H16O3N2Cl [M+H]+ 295.0844, Found 295.0843。
Embodiment 19: (E) -4- chloro-acetophenone oxime 0.1775g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- chlorphenyl) -1- acetophenone oxime ether.White solid, yield: 79%, fusing point 74.8- 75.2℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.51 – 7.46 (m, 2H), 7.34 – 7.28 (m, 2H), 5.11 (dd, J = 8.4, 4.0 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.4 Hz, 1H), 2.94 (dd, J = 18.3, 3.9 Hz, 1H), 2.26 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.71, 174.37, 156.76, 135.79, 133.95, 128.65, 127.44, 76.05, 35.25, 33.84, 12.98, 12.84.
UV-vis (CH3CN) λmax/nm 253；
FT-IR ν/cm-1 (KBr):3711, 3472, 3066, 2976, 2941, 1707, 1594, 1454, 1406, 1344, 1219, 1116, 1039, 887, 807, 689;
MALDI-FTICR MS m/z Calcd for C14H16O3N2Cl [M+H]+ 295.0844, Found 295.0841。
Embodiment 20: (E) -3- bromoacetophenone oxime 0.2226g (1.05 mmol), N- ethyl are added in test tube along fourth Alkene imidodicarbonic diamide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) set test tube progress nitrogen After changing, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(3- bromophenyl) -1- acetophenone oxime ether.Yellow oil, yield: 82%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.70 (t, J = 1.8 Hz, 1H), 7.52 – 7.45 (m, 2H), 7.22 (t, J = 7.9 Hz, 1H), 5.12 (dd, J = 8.4, 4.0 Hz, 1H), 3.64 (q, J = 7.2 Hz, 2H), 3.06 (dd, J = 18.4, 8.4 Hz, 1H), 2.94 (dd, J = 18.4, 4.0 Hz, 1H), 2.26 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.64, 174.31, 156.40, 137.46, 132.57, 129.94, 129.13, 124.73, 122.57, 76.14, 35.25, 33.82, 12.98, 12.80.
UV-vis (CH3CN) λmax/nm 254；
FT-IR ν/cm-1 (KBr):3741, 3477, 3068, 2982, 2941, 1711, 1623, 1558, 1448, 1406, 1347, 1230, 1126, 1064, 1035, 896, 787, 689, 531;
MALDI-FTICR MS m/z Calcd for C14H17O3N2Br [M+H]+ 339.0339, Found 339.0337。
Embodiment 21: addition (E) -4- bromoacetophenone oxime 0.2226g (1.05 mmol), N- ethyl are suitable in test tube Butylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- bromophenyl) -1- acetophenone oxime ether.White solid, yield: 56%, fusing point 68.2- 68.7℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.49 – 7.40 (m, 4H), 5.11 (dd, J = 8.4, 4.0 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.05 (dd, J = 18.4, 8.4 Hz, 1H), 2.94 (dd, J = 18.4, 4.0 Hz, 1H), 2.26 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.70, 174.36, 156.85, 134.42, 131.61, 127.69, 124.12, 76.06, 35.25, 33.85, 12.98, 12.80.
UV-vis (CH3CN) λmax/nm 259；
FT-IR ν/cm-1 (KBr):3477, 3062, 2966, 2936, 1706, 1587, 1451, 1405, 1343, 1218, 1114, 890, 807, 684, 540;
MALDI-FTICR MS m/z Calcd for C14H17O3N2Br [M+H]+ 339.0339, Found 339.0336。
Embodiment 22: (E) -4- phenylacetophenone oxime 0.2216g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- xenyl) -1- acetophenone oxime ether.White solid, yield: 66%, fusing point 114.8- 115.5℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.64 (d, J = 8.5 Hz, 2H), 7.61 – 7.56 (m, 4H), 7.45 (t, J = 7.7 Hz, 2H), 7.39 – 7.34 (m, 1H), 5.13 (dd, J = 8.2, 4.1 Hz, 1H), 3.65 (q, J = 7.2 Hz, 2H), 3.07 (dd, J = 18.4, 8.3 Hz, 1H), 2.99 (dd, J = 18.4, 4.1 Hz, 1H), 2.32 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.88, 174.53, 157.47, 142.49, 140.25, 134.41, 128.86, 127.71, 127.09, 127.05, 126.62, 76.02, 35.32, 33.85, 13.02, 12.93.
UV-vis (CH3CN) λmax/nm 279；
FT-IR ν/cm-1 (KBr):3488, 3033, 2985, 2941, 1707, 1607, 1445, 1408, 1346, 1226, 1123, 1030, 840, 761, 687;
MALDI-FTICR MS m/z Calcd for C20H21O3N2 [M+H]+ 337.1547, Found 337.1543。
Embodiment 23: (E) -3- nitro-acetophenone oxime 0.1890g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(3- nitrobenzophenone) -1- acetophenone oxime ether.White solid, yield: 61%, fusing point 96.9-97.4℃.Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 8.41 (t, J = 2.0 Hz, 1H), 8.23 (ddd, J = 8.2, 2.3, 1.1 Hz, 1H), 7.90 (dt, J = 7.7, 1.3 Hz, 1H), 7.54 (t, J = 8.0 Hz, 1H), 5.17 (dd, J = 8.5, 3.9 Hz, 1H), 3.65 (q, J = 7.2 Hz, 2H), 3.10 (dd, J = 18.4, 8.5 Hz, 1H), 2.94 (dd, J = 18.4, 3.9 Hz, 1H), 2.34 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.42, 174.10, 155.77, 148.38, 137.17, 131.81, 129.48, 124.29, 121.14, 76.36, 35.26, 33.95, 12.98, 12.86.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3750, 3470, 3070, 2987, 2946, 1702, 1624, 1530, 1448, 1408, 1348, 1228, 1129, 1018, 906, 778, 682;
MALDI-FTICR MS m/z Calcd for C14H16O5N3 [M+H]+ 306.1084, Found 306.1083。
Embodiment 24: (E) -4- nitro-acetophenone oxime 0.1890g (1.05 mmol), N- ethyl are added in test tube Maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After gas displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(N- Ethyl -2,5- dicarbapentaborane pyrrolidinyl) -1-(4- nitrobenzophenone) -1- acetophenone oxime ether.Yellow solid, yield: 61%, fusing point 154.7-155.5℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 8.22 – 8.16 (m, 1H), 7.75 – 7.69 (m, 1H), 5.18 (dd, J = 8.5, 3.9 Hz, 0H), 3.63 (q, J = 7.2 Hz, 1H), 3.09 (dd, J = 18.4, 8.5 Hz, 0H), 2.93 (dd, J = 18.4, 4.0 Hz, 0H), 2.32 (s, 1H), 1.20 (t, J = 7.2 Hz, 1H).
13C NMR (126 MHz, CDCl3) δ 174.35, 174.06, 156.03, 148.42, 141.41, 127.01, 123.66, 76.42, 35.22, 33.91, 12.98, 12.93.
UV-vis (CH3CN) λmax/nm 300；
FT-IR ν/cm-1 (KBr):3736, 3060, 2994, 2947, 1712, 1570, 1519, 1449, 1405, 1346, 1230, 1102, 1032, 897, 854, 688;
MALDI-FTICR MS m/z Calcd for C14H16O5N3 [M+H]+ 306.1084, Found 306.1083。
Embodiment 25: addition (E)-phenylpropyl alcohol ketoxime 0.1565g (1.05 mmol), N- ethyl are suitable in test tube Butylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), carry out nitrogen for test tube After displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NSecond Base -2,5- dicarbapentaborane pyrrolidinyl) -1- phenyl -1- acetoxime ether.Yellow oil, yield: 89%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.59 – 7.47 (m, 2H), 7.37 – 7.28 (m, 3H), 5.09 (dd, J = 8.2, 4.0 Hz, 1H), 3.61 (q, J = 7.2 Hz, 2H), 3.03 (dd, J = 18.3, 8.3 Hz, 1H), 2.95 (dd, J = 18.3, 4.0 Hz, 1H), 2.78 (qd, J = 7.6, 4.0 Hz, 2H), 1.19 (t, J = 7.2 Hz, 3H), 1.15 (t, J = 7.6 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.85, 174.56, 162.70, 134.52, 129.65, 128.47, 126.39, 75.90, 35.20, 33.78, 20.23, 12.96, 11.12.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3740, 3478, 3056, 2980, 2943, 1710, 1612, 1571, 1451, 1404, 1344, 1230, 1126, 1029, 913, 877, 765, 694;
MALDI-FTICR MS m/z Calcd for C15H19O3N2 [M+H]+ 275.1390, Found 275.1389。
Embodiment 26: (E)-2- methyl-1-phenylpropyl alcohol ketoxime 0.1712g (1.05 mmol), N- is added in test tube Ethylmaleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), by test tube into After the displacement of row nitrogen, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl-2,5- dicarbapentaborane pyrrolidinyl)-1- phenyl-2- methyl-1-acetoxime ether.Grease, yield: 71%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.43 – 7.31 (m, 4H), 7.29 – 7.25 (m, 1H), 5.08 (dd, J = 8.3, 4.1 Hz, 0.5H), 4.87 (t, J = 6.1 Hz, 0.5H), 3.60 (p, J = 7.2 Hz, 2H), 3.52 (p, J = 7.1 Hz, 0.5H), 3.03 (dd, J = 18.3, 8.3 Hz, 0.5H), 2.94 (dd, J = 18.3, 4.1 Hz, 1.5H), 2.78 (p, J = 6.9 Hz, 0.5H), 1.20 (t, J = 7.1 Hz, 4.5H), 1.17 (t, J = 7.2 Hz, 1.5H), 1.05 (dd, J = 14.2, 6.8 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.73, 174.43, 167.31, 134.94, 133.35, 128.10, 127.74, 75.87, 34.85, 33.74, 28.56, 19.83, 19.48, 12.89.
UV-vis (CH3CN) λmax/nm 250；
FT-IR ν/cm-1 (KBr):3740, 3355, 2975, 2930, 1710, 1567, 1449, 1402, 1345, 1231, 1085, 1049, 886, 770, 695;
MALDI-FTICR MS m/z Calcd for C16H21O3N2 [M+H]+ 289.1547, Found 289.1545。
Embodiment 27: (E) -1,2- diphenylethan oxime 0.2216g (1.05 mmol), N- second are added in test tube Base maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), test tube is carried out After nitrogen displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO- (NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -1- phenyl -2- phenyl -1- acetophenone oxime ether.White solid, yield: 59%, fusing point: 96.6-96.8℃。
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.57 – 7.54 (m, 2H), 7.36 – 7.24 (m, 5H), 7.24 – 7.17 (m, 3H), 5.14 (dd, J = 8.3, 4.0 Hz, 1H), 4.18 (s, 2H), 3.64 (q, J = 7.2 Hz, 2H), 3.04 (dd, J = 18.3, 8.3 Hz, 1H), 2.95 (dd, J = 18.3, 4.1 Hz, 1H), 1.22 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.64, 174.41, 159.25, 135.99, 134.65, 129.80, 128.71, 128.47, 128.38, 126.69, 126.52, 76.11, 35.19, 33.86, 32.82, 12.99.
UV-vis (CH3CN) λmax/nm 252；
FT-IR ν/cm-1 (KBr):3743, 3470, 3064, 2990, 2946, 1706, 1601, 1499, 1445, 1407, 1346, 1229, 1127, 1025, 891, 764, 691;
MALDI-FTICR MS m/z Calcd for C20H21O3N2 [M+H]+ 337.1547, Found 337.1543。
Embodiment 28: diphenyl-ketoxime 0.1712g (1.05 mmol), N- ethyl maleic two are added in test tube Test tube is carried out nitrogen displacement by acid imide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) Afterwards, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl- 2,5- dicarbapentaborane pyrrolidinyl) -1,1- diphenyl -1- ketoxime ether.White solid, yield: 64%, fusing point: 128.9-129.3 DEG C.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.48 – 7.42 (m, 3H), 7.41 – 7.36 (m, 5H), 7.33 – 7.28 (m, 2H), 5.05 (dd, J = 7.0, 5.5 Hz, 1H), 3.63 (q, J = 7.2 Hz, 2H), 3.04 (s, 1H), 3.02 (d, J = 2.0 Hz, 1H), 1.21 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.71, 174.50, 159.82, 135.50, 132.31, 130.01, 129.31, 129.26, 128.27, 128.18, 128.13, 76.19, 34.96, 33.85, 12.97.
UV-vis (CH3CN) λmax/nm 260；
FT-IR ν/cm-1 (KBr):3483, 3053, 2982, 2942, 1713, 1595, 1440, 1402, 1348, 1224, 1120, 1030, 904, 774, 699;
MALDI-FTICR MS m/z Calcd for C19H19O3N2 [M+H]+ 323.1390, Found 323.1388。
Embodiment 29: (E)-(2- thienyl) acetophenone oxime 0.1481g (1.05 mmol), N- second are added in test tube Base maleimide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol), test tube is carried out After nitrogen displacement, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO- (NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -1- thienyl -1- acetophenone oxime ether.Yellow oil, yield: 71%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.27 (dd, J = 5.1, 1.1 Hz, 1H), 7.23 (dd, J = 3.7, 1.2 Hz, 1H), 6.99 (dd, J = 5.1, 3.7 Hz, 1H), 5.05 (dd, J = 8.2, 3.9 Hz, 1H), 3.62 (q, J = 7.1 Hz, 2H), 3.02 (dd, J = 18.4, 8.2 Hz, 1H), 2.93 (dd, J = 18.4, 3.9 Hz, 1H), 2.28 (s, 3H), 1.23 (t, J = 7.3 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.77, 174.48, 153.61, 127.81, 127.20, 126.98, 125.78, 75.95, 35.20, 33.84, 13.14, 13.04.
UV-vis (CH3CN) λmax/nm 266,283；
FT-IR ν/cm-1 (KBr):3740, 3482, 3098, 2980, 2941, 1710, 1602, 1444, 1406, 1346, 1229, 1126, 893, 803, 719;
MALDI-FTICR MS m/z Calcd for C12H15O3N2S [M+H]+ 267.0798, Found 267.0796。
Embodiment 30: dibenzyl ketone oxime 0.2363g (1.05 mmol), N- ethyl maleic two are added in test tube Test tube is carried out nitrogen displacement by acid imide 0.0750g (0.6 mmol), copper acetate monohydrate 0.0240g (0.12 mmol) Afterwards, 2mL o-dichlorohenzene is added, 75 DEG C are reacted 8 hours, are cooled and separated and are obtained target product (E)-after purificationO(NEthyl- 2,5- dicarbapentaborane pyrrolidinyl) -1,1- dibenzyl -1- ketoxime ether.Yellow oil, yield: 43%.
Structural formula:
1H NMR (500 MHz, Chloroform-d) δ 7.31 – 7.26 (m, 4H), 7.25 – 7.20 (m, 2H), 7.14 – 7.07 (m, 4H), 5.06 (dd, J = 8.3, 4.1 Hz, 1H), 3.62(q, J = 7.5 Hz, 2H), 3.61 (s, 2H), 3.37 (s, 2H), 3.04 (dd, J = 18.3, 8.3 Hz,1H), 2.94 (dd, J = 18.3, 4.1 Hz, 1H), 1.19 (t, J = 7.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 174.90, 174.47, 161.39, 136.03, 135.71, 129.15, 129.09, 128.68, 128.61, 126.88, 126.70, 75.63, 39.47, 35.09, 33.83, 33.33, 12.97.
UV-vis (CH3CN) λmax/nm 259；
FT-IR ν/cm-1 (KBr):3742, 3471, 3059, 2990, 2930, 1710, 1596, 1493, 1445, 1403, 1344, 1219, 1097, 1034, 909, 749, 698;
MALDI-FTICR MS m/z Calcd for C21H23O3N2 [M7777+H]+ 351.1703, Found 351.1701。

Claims (4)

1. a kind ofO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives, it is characterised in that the structure of the derivative Formula are as follows:
In formula:
R1Are as follows: phenyl, substituted-phenyl, benzyl or thienyl；
R2Are as follows: phenyl, C1-C3Alkyl or benzyl.
2. it is a kind of prepare it is according to claim 1O-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives Method, it is characterised in that the specific steps of this method are as follows: by compound 1 and compound 2 and transition-metal catalyst by (1.5 ~ 1.75) molar ratio: 1:(0.15 ~ 0.2) is dissolved in organic solvent, is reacted 8 ~ 10 hours at 75 ~ 90 DEG C；It is cooled and separated It obtains after purificationO-(NEthyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives；The structural formula of the compound 1 are as follows:；The structural formula of the compound 2 are as follows:。
3. according to the method described in claim 2, it is characterized in that the transition-metal catalyst are as follows: Cu (OAc)2 ·H2O 、 Cu、Cu(OAc)2, CuCl or CuI.
4. according to the method described in claim 2, it is characterized in that the organic solvent is o-dichlorohenzene, toluene, dimethyl Asia Sulfone or N,N-dimethylformamide.
CN201811154777.8A 2018-09-30 2018-09-30 O-(N- ethyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof Pending CN109280025A (en)

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JP2011012088A (en) * 2010-08-10 2011-01-20 Nippon Soda Co Ltd Oxime compound or salt thereof, and fungicide

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JP2011012088A (en) * 2010-08-10 2011-01-20 Nippon Soda Co Ltd Oxime compound or salt thereof, and fungicide

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CN110642748A (en) * 2019-09-20 2020-01-03 华南理工大学 O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and synthetic method and application thereof

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