CN104072421B - Chiral imidazoline sulfur ligand and synthesis method thereof - Google Patents
Chiral imidazoline sulfur ligand and synthesis method thereof Download PDFInfo
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a chiral imidazoline sulfur ligand and a synthesis method thereof. The synthesis method comprises the following steps: adopting 1-bromine-2-imidazoline benzene or 1-bromine-2-imidazoline naphthalene as a starting material; treating the starting material with n-BuLi, and conducting reaction on the starting materials with diphenyl dithioether; adding 10% of a NaOH solution; carrying out extraction; carrying out drying; carrying out concentration; carrying out chromatograph to obtain the novel chiral imidazoline sulfur ligand. The synthesis method provides a simple and feasible method for synthesis of chiral imidazoline sulfur ligand, and provides convenience for research and wide application of the chiral imidazoline sulfur ligand; besides, the compound can be used for an asymmetric catalytic reaction as a chiral ligand.
Description
Technical field
The present invention relates to organic compound synthesis and applied technical field, particularly a kind of chiral imidazole quinoline sulfur part and conjunction
One-tenth method.
Background technology
In 19 century 70s, Jame the first in the group time reports chiral sulphur compound and can join as potential chirality
Body, with rhodium, ruthenium is as metal salt back alkene, and has obtained the result (J.Mol.Catal.1976, Isosorbide-5-Nitrae 39.) envisioned.With
Afterwards, much chiral sulfur parts are had to be reported.They are mainly used in the formation of asymmetric C-C key, particularly take in nucleophilic allyl group
Application in generation reaction, also D-A reaction, Heck reacts, (the list of references such as asymmetric conjugated reaction reaction：(a)
Angew.Chem.Int.Ed.2000,39,3558, (b) J.Org.Chem.2004,69,8062, (c)
Eur.J.Org.Chem.2002,3221.).
In numerous chiral ligands being connected with P, N, O, S and other coordination atom, the cooperation of containing n-donor ligand and transition metal
Thing also increasingly shows its importance in some asymmetric catalysis.In containing n-donor ligand, oxazolines be wherein than
A more prominent class, be easily obtained because of it, applied widely the features such as and become the extremely successful part of a class
(Chem.Rev.2004,104,4151), imidazoline is similar to oxazoline, and imidazoline is the five-ring heterocycles containing two N atoms
On compound, wherein imines, N atom is good coordination atom, can be coordinated well with metal, and another N atom on imidazoline
The sterically hindered of whole part and electronic effect can be regulated and controled by modifying its substituent group.Therefore, chiral imidazole in recent years
The synthesis of quinoline and application cause chemists widely interest (list of references (a) Adv.Synth.Catal.2008,350,
1443, (b) Chem.Eur.J.2010,16,2360, (c) Angew.Chem.Int.Ed.2012,51,10337, (d)
Organometallics2013,32,3544. (e) Org.Lett.2014,16,1700).
In addition, many S, the series part such as S-, S, P-, S, N- has obtained widely should in asymmetric catalysis
With.Especially prominent (the list of references of application of especially oxazoline sulfur (S, N-) part：(a) Tetrahedron Lett.1993,
34,7793. (b) Chem.Commun.1998,2765 (c) Synlett1999,1319. (d) Tetrahedron Lett.2002,
43,4907. (e) Tetrahedron：Asymmetry2010,21,241.) it is excellent, to have that selectivity is high and reaction condition is gentle etc.
Point.And the synthesis of chiral imidazole quinoline sulfur (S, N-) part and application less, only several report ((a) Synlett1997,785.
(b) Tetrahedron Lett.2002,44,1971. (c) Eur.J.Org.Chem.2011,786.).
Content of the invention
The invention aims to providing a kind of chiral imidazole quinoline sulfur part and synthetic method.
For reaching above-mentioned purpose, the present invention is to implement according to technical scheme below：
A kind of chiral imidazole quinoline sulfur part, its general structure is：
Wherein R1For p-methylphenyl, cyclohexyl, C1-C10Alkyl or aryl；R2For i-Pr, t-Bu, Ph or Bn.
A kind of synthetic method of chiral imidazole quinoline sulfur part, comprises the following steps：
1) under anhydrous and oxygen-free inert gas shielding, bromo- for 1- 2- imidazoline benzene or 1- bromo- 2- imidazoline naphthalene are dissolved in tetrahydrochysene
Furan, when temperature is adjusted to -78 DEG C, is initially charged n-BuLi reaction half an hour, adds Diphenyl disulfide ether, continue low temperature
Reaction 3-6 hour, moves to room temperature and processes；
2) add 10% NaOH solution that reaction is quenched, after being extracted with ethyl acetate, use anhydrous Na2SO4It is dried, concentrate；
3) with ethyl acetate or dichloromethane and methanol as developing solvent, chiral imidazole quinoline sulfur is obtained by chromatographic isolation and joins
Body；
Further, described step 1) in 1- bromo- 2- imidazoline benzene or 1- bromo- 2- imidazoline naphthalene: n-BuLi: diphenyl
Disulfide=1: 1-2: 1-2.
As the preferred version of the present invention, described step 1) in noble gases be argon.
Compared with prior art, the present invention is that synthesis imidazoline sulfur part provides a simplicity, easy method；Separately
Outward, chiral imidazole quinoline sulfur part also can be applied in asymmetric catalysis as chiral ligand.
Specific embodiment
With reference to specific embodiment, the invention will be further described, illustrative examples and explanation that here is invented
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
The preparation of 2- ((S) -4- isopropyl -1- p-methylphenyl -1H- imidazoline -2- base) diphenyl sulfide：History Lay in 50mL
1- ((S) -4- isopropyl -1- p-methylphenyl -1H- imidazoline -2- base) -2- bromobenzene (440mg, 1.23mmol) is added in gram pipe,
Under argon protection, add the dissolving of 20mL anhydrous tetrahydro furan, Shrek pipe is put in -78 DEG C of cold hydrazines, under stirring, solution is cold
But to -78 DEG C.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, inject dissolving with syringe
The 10mL anhydrous tetrahydrofuran solution of PhSSPh (402mg, 1.85mmol), continues three hours of stirring.Then from -78 DEG C of cold hydrazines
Middle taking-up Shrek pipe, after being naturally warmed to room temperature, adds 10% NaOH solution, is extracted with ethyl acetate, saturated aqueous common salt
Washing, anhydrous Na2SO4It is dried, filtering and concentrating, pillar layer separation (eluant: ethyl acetate/petroleum ether=1: 2).Obtain light yellow
Oily compound.Yield is 84%.[α]20 D=-36.6 ° of (c=0.478mg/100mL in CHCl3).TLC：Rf=0.2
(ethyl acetate: petroleum ether=1: 2).1H NMR (400MHz, CDCl3)：δ (ppm) 7.44-7.41 (m,
1H), 7.24-7.23 (m, 3H), 7.16-7.15 (m, 4H), 6.99-6.97 (m, 1H), 6.91 (d, J=8.0Hz, 2H), 6.65
(d, J=8.0Hz, 2H), 4.08-3.96 (m, 2H), 3.69 (appt, J=8.0Hz, 1H), 2.23 (s, 3H), 1.97-1.92
(m, 1H), 1.07 (d, J=8.0Hz, 3H), 1.00 (d, J=8.0Hz, 3H).13C NMR (100MHz, CDCl3)：δ(ppm)
160.0,139.2,136.9,134.8,132.8,132.7,132.2,130.5,129.9,129.8,129.2,129.1,
127.5,126.2,120.6,70.4,54.3,33.0,20.7,19.0,18.3.HRMS (m/z, ESI+) found for M+H=
387.1892, C25H27N2S requires387.1895.
Embodiment 2
The preparation of 2- ((the S) -4- tert-butyl group -1- p-methylphenyl -1H- imidazoline -2- base) diphenyl sulfide：History Lay in 50mL
1- ((the S) -4- tert-butyl group -1- p-methylphenyl -1H- imidazoline -2- base) -2- bromobenzene (492mg, 1.23mmol) is added in gram pipe,
Under argon protection, add the oxolane dissolving that 20mL Non-aqueous processing is crossed, Shrek pipe is put in -78 DEG C of cold hydrazines, under stirring
Solution is cooled to -78 DEG C.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, noted with syringe
Enter to dissolve the 10mL anhydrous tetrahydrofuran solution of PhSSPh (402mg, 1.85mmol), continue three hours of stirring.Then from -78
Take out Shrek pipe in DEG C cold hydrazine, after being naturally warmed to room temperature, add 10% NaOH solution, be extracted with ethyl acetate, saturation
Brine It, anhydrous Na2SO4It is dried, filtering and concentrating, pillar layer separation (eluant: ethyl acetate/petroleum ether=1: 2).?
Pale yellowish oil compound.Yield is 72%, [α]20 D=-18.1 ° of (c=0.503mg/100mL in CHCl3).TLC：Rf=
0.3 (ethyl acetate: petroleum ether=1: 2).1H NMR (400MHz, CDCl3)：δ(ppm)7.43-7.41
(m, 1H), 7.25-7.24 (m, 3H), 7.18-7.13 (m, 4H), 6.97-6.95 (m, 1H), 6.92 (d, J=8.4Hz, 2H),
6.67 (d, J=8.4Hz, 2H), 3.99-3.98 (m, 2H), 3.72 (appt, J=2.8Hz, 1H), 2.24 (s, 3H), 1.03 (s,
9H).13C NMR (100MHz, CDCl3)：δ (ppm) 160.2,139.4,137.2,134.8,132.9,132.6,132.3,
130.4,129.9,129.8,129.2,129.1,127.6,126.1,120.9,74.2,53.2,34.2,26.2,20.7.HRMS
(m/z, ESI+), found for M+H=401.2049, C26H29N2S requires401.2051.
Embodiment 3
The preparation of 2- ((S) -4- phenyl -1- p-methylphenyl -1H- imidazoline -2- base) diphenyl sulfide：Shrek in 50mL
1- ((S) -4- phenyl -1- p-methylphenyl -1H- imidazoline -2- base) -2- bromobenzene (517mg, 1.23mmol), argon is added in pipe
Under protection, add the dissolving of 20mL anhydrous tetrahydro furan, Shrek pipe is put in -78 DEG C of cold hydrazines, under stirring, solution is cooled to -
78℃.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, inject PhSSPh with syringe
The 10mL anhydrous tetrahydrofuran solution of (402mg, 1.85mmol), continues three hours of stirring.Then take out from -78 DEG C of cold hydrazines
Shrek pipe, after being naturally warmed to room temperature, adds 10% NaOH solution, is extracted with ethyl acetate, saturated common salt water washing, no
Water Na2SO4It is dried, filtering and concentrating, pillar layer separation (ethyl acetate: petroleum ether=1: 2).Obtain white solid
Body.Yield 52%, mp：45-46 DEG C, [α]20 D=-75.5 ° of (c=0.707mg/100mL in CHCl3).TLC：Rf=0.3
(ethyl acetate: petroleum ether=1: 2).1H NMR (400MHz, CDCl3)：δ (ppm) 7.55-7.53 (m,
1H), 7.43 (d, J=7.2Hz, 2H), 7.32 (t, J=7.2Hz, 2H), 7.24-7.20 (m, 6H), 7.14-7.12 (m, 2H),
7.05-7.03 (m, 1H), 6.91 (d, J=8.0Hz, 2H), 6.68 (d, J=8.4Hz, 2H), 5.33 (app t, J=10.0Hz,
1H), 4.35 (dd, J=9.2,10.4Hz, 1H), 3.93 (app t, J=9.2Hz, 1H), 2.23 (s, 3H).13C NMR
(100MHz, CDCl3)：δ (ppm) 161.5,143.9,138.8,136.4,134.9,132.9,132.7,132.3,131.1,
130.1,130.0,129.3,129.2,128.5,127.4,127.15,127.09,126.6,120.8,67.9,59.9,
20.7.HRMS (m/z, ESI+), found for M+H=421.1739, C28H25N2S requires421.1738.
Embodiment 4
The preparation of 2- ((S) -4- isopropyl -1- p-methylphenyl -1H- imidazoline -2- base) -1- naphthalene diphenyl sulfide：50mL's
In Shrek pipe add 2- ((S) -4- isopropyl -1- p-methylphenyl -1H- imidazoline -2- base) -1- bromonaphthalene (500mg,
1.23mmol), under argon protection, add the dissolving of 20mL anhydrous tetrahydro furan, Shrek pipe is put in -78 DEG C of cold hydrazines, stirring
Lower solution is cooled to -78 DEG C.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, use syringe
The 10mL anhydrous tetrahydrofuran solution of injection PhSSPh (402mg, 1.85mmol), continues three hours of stirring.Then from -78 DEG C
Take out Shrek pipe in cold hydrazine, after being naturally warmed to room temperature, add 10% NaOH solution, be extracted with ethyl acetate, saturation is eaten
Salt water washing, anhydrous Na2SO4It is dried, filtration is evaporated, pillar layer separation, eluent is petroleum ether: ethyl acetate=2: 1.Separate
Light yellow solid Compound is obtained, yield is 40% after purification.mp：119-120 DEG C, [α]20 D=-4.4 ° of (c=0.413mg/
100mL in CHCl3).TLC：Rf=0.2 (petroleum ether: ethyl acetate=2: 1).1H NMR (400MHz,
CDCl3)：δ (ppm) 8.24 (d, J=8.4Hz, 1H), 7.96 (d, J=8.4Hz, 1H), 7.85 (d, J=8.0Hz, 1H), 7.71
(d, J=8.4Hz, 1H), 7.49-7.47 (m, 1H), 7.42-7.38 (m, 1H), 7.03-6.94 (m, 3H), 6.86-6.84 (m,
2H), 6.74 (d, J=8.4Hz, 2H), 6.56 (d, J=8.4Hz, 2H), 4.07-4.01 (m, 1H), 3.97 (brs, 1H), 3.75
(brs, 1H), 2.13 (s, 3H), 1.93-1.88 (m, 1H), 1.01 (d, J=6.8Hz, 3H), 0.96 (d, J=6.8Hz, 3H)
.13C NMR (100MHz, CDCl3)：δ (ppm) 160.9,138.5,137.5,134.4,134.3,132.0,130.4,129.2,
128.6,128.5,127.4,127.2,127.0,126.9,124.9,120.2,54.0,33.0,20.6,19.0,18.2.HRMS
(m/z, ESI+), found for M+H=437.2051, C29H29N2S requires437.2051.
Embodiment 5
The preparation of 2- ((the S) -4- tert-butyl group -1- p-methylphenyl -1H- imidazoline -2- base) -1- naphthalene diphenyl sulfide：50mL's
In Shrek pipe add 2- ((the S) -4- tert-butyl group -1- p-methylphenyl -1H- imidazoline -2- base) -1- bromonaphthalene (553mg,
1.23mmol), under argon protection, add the dissolving of 20mL anhydrous tetrahydro furan, Shrek pipe is put in -78 DEG C of cold hydrazines, stirring
Lower solution is cooled to -78 DEG C.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, use syringe
The 10mL anhydrous tetrahydrofuran solution of injection PhSSPh (402mg, 1.85mmol), continues three hours of stirring.Then from -78 DEG C
Take out Shrek pipe in cold hydrazine, after being naturally warmed to room temperature, add 10% NaOH solution, be extracted with ethyl acetate, saturation is eaten
Salt water washing, anhydrous Na2SO4It is dried, filtration is evaporated, pillar layer separation, eluent is petroleum ether: ethyl acetate=2: 1.Separate
Light yellow solid Compound is obtained, yield is 33% after purification.mp：66-68 DEG C, [α]20 D=+31.2 ° of (c=0.529mg/100mL
in CHCl3).TLC：Rf=0.2 (petroleum ether: ethyl acetate=2: 1).1H NMR (400MHz,
CDCl3)：δ (ppm) 8.23 (d, J=8.4Hz, 1H), 7.96 (d, J=8.4Hz, 1H), 7.85 (d, J=8.0Hz, 1H), 7.71
(d, J=8.4Hz, 1H), 7.49-7.45 (m, 1H), 7.42-7.37 (m, 1H), 7.02-6.94 (m, 3H), 6.83-6.80 (m,
2H), 6.74 (d, J=8.4Hz, 2H), 6.58 (d, J=8.4Hz, 2H), 3.97 (brs, 2H), 3.81 (brs, 1H), 2.12 (s,
3H), 0.97 (s, 9H).13C NMR (100MHz, CDCl3)：δ (ppm) 161.1,138.4,137.6,134.4,134.3,
132.2,130.5,129.2,128.6,128.5,127.5,127.0,126.9,124.8,120.5,52.9,34.2,26.2,
20.6.HRMS (m/z, ESI+), found for M+H=451.2205, C30H31N2S requires451.2208.
Embodiment 6
The preparation of 2- ((S) -4- phenyl -1- p-methylphenyl -1H- imidazoline -2- base) -1- naphthalene diphenyl sulfide：History in 50mL
2- ((S) -4- phenyl -1- p-methylphenyl -1H- imidazoline -2- base) -1- bromonaphthalene (578mg, 1.23mmol) is added in the pipe of Rec,
Under argon protection, add the dissolving of 20mL anhydrous tetrahydro furan, Shrek pipe is put in -78 DEG C of cold hydrazines, the lower solution cooling of stirring
To -78 DEG C.It is slowly injected into n-BuLi (0.98mL, 2.46mmol) with syringe, after a hour, inject PhSSPh with syringe
The 10mL anhydrous tetrahydrofuran solution of (402mg, 1.85mmol), continues three hours of stirring.Then take out from -78 DEG C of cold hydrazines
Shrek pipe, after being naturally warmed to room temperature, adds 10% NaOH solution, is extracted with ethyl acetate, saturated common salt water washing, no
Water Na2SO4It is dried, filtration is evaporated, pillar layer separation, eluent is petroleum ether: ethyl acetate=2: 1.Obtain pale yellow after separating-purifying
Color solid chemical compound, yield is 27%.mp：77-78 DEG C, [α]20 D=-108.0 ° of (c=0.650mg/100mL in CHCl3)
.TLC：Rf=0.2 (petroleum ether: ethyl acetate=2: 1).1H NMR (400MHz, CDCl3)：δ(ppm)
8.27 (d, J=8.4Hz, 1H), 8.02 (d, J=8.4Hz, 1H), 7.88 (d, J=8.0Hz, 1H), 7.82 (d, J=8.4Hz,
1H), 7.51-7.47 (m, 1H), 7.44-7.40 (m, 1H), 7.31 (brs, 2H), 7.22 (brs, 3H), 7.06-6.97 (m,
3H), 6.86 (d, J=7.2Hz, 2H), 6.76 (d, J=8.4Hz, 2H), 6.58 (d, J=8.4Hz, 2H), 5.33 (app t, J
=10.0Hz, 1H), 4.32 (brs, 1H), 4.00 (brs, 1H), 2.12 (s, 3H).13C NMR (100MHz, CDCl3)：δ(ppm)
162.3,143.8,138.0,137.4,134.6,134.3,132.5,130.7,129.3,128.8,128.7,128.4,
127.6,127.1,126.9,125.0,120.4,59.6,29.8,20.7.HRMS (m/z, ESI+), foundfor M+H=
471.1891, C32H27N2S requires471.1895.
Technical scheme is not limited to the restriction of above-mentioned specific embodiment, and every technology according to the present invention scheme is done
The technology deformation going out, each falls within protection scope of the present invention.
Claims (1)
1. a kind of synthetic method of chiral imidazole quinoline sulfur part is it is characterised in that comprise the following steps：
1) under anhydrous and oxygen-free inert gas shielding, bromo- for 1- 2- imidazoline benzene or 1- bromo- 2- imidazoline naphthalene are dissolved in tetrahydrochysene furan
Mutter, when temperature is adjusted to -78 DEG C, is initially charged n-BuLi reaction half an hour, adds Diphenyl disulfide ether, continue low temperature anti-
Answer 3-6 hour, move to room temperature and process；
2) add 10% NaOH solution that reaction is quenched, after being extracted with ethyl acetate, use anhydrous Na2SO4It is dried, concentrate；
3) with ethyl acetate or dichloromethane and methanol as developing solvent, chiral imidazole quinoline sulfur part is obtained by chromatographic isolation；
Described chiral imidazole quinoline sulfur part, its general structure is：
Wherein R1For p-methylphenyl, cyclohexyl, C1-C10Alkyl or aryl；R2For i-Pr, t-Bu, Ph or Bn；
Described step 1) in 1- bromo- 2- imidazoline benzene or 1- bromo- 2- imidazoline naphthalene: n-BuLi: Diphenyl disulfide ether=1: 1-2
∶1-2；
Described step 1) in noble gases be argon.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005058917A2 (en) * | 2003-12-17 | 2005-06-30 | The Penn State Research Foundation | New oxazoline ligands for asymmetric catalysis |
| CN1842533A (en) * | 2003-08-29 | 2006-10-04 | 索尔维亚斯股份公司 | Phospinite-imidazolines and metal complexes thereof |
| US20080132550A1 (en) * | 2003-07-21 | 2008-06-05 | Aventis Pharmaceuticals Inc. | Heterocyclic compounds as p2x7 ion channel blockers |
| CN101962366A (en) * | 2010-09-15 | 2011-02-02 | 北京理工大学 | Diphenyl thioether linked bis-imidazoline ligand compound and preparation method thereof |
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2014
- 2014-07-14 CN CN201410333636.8A patent/CN104072421B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080132550A1 (en) * | 2003-07-21 | 2008-06-05 | Aventis Pharmaceuticals Inc. | Heterocyclic compounds as p2x7 ion channel blockers |
| CN1842533A (en) * | 2003-08-29 | 2006-10-04 | 索尔维亚斯股份公司 | Phospinite-imidazolines and metal complexes thereof |
| WO2005058917A2 (en) * | 2003-12-17 | 2005-06-30 | The Penn State Research Foundation | New oxazoline ligands for asymmetric catalysis |
| CN101962366A (en) * | 2010-09-15 | 2011-02-02 | 北京理工大学 | Diphenyl thioether linked bis-imidazoline ligand compound and preparation method thereof |
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