CN109320539A - Spiral shell benzoxazine or spiral shell naphtho- oxazines and isoquinolin indolinone derivative and its synthetic method - Google Patents
Spiral shell benzoxazine or spiral shell naphtho- oxazines and isoquinolin indolinone derivative and its synthetic method Download PDFInfo
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- CN109320539A CN109320539A CN201811186335.1A CN201811186335A CN109320539A CN 109320539 A CN109320539 A CN 109320539A CN 201811186335 A CN201811186335 A CN 201811186335A CN 109320539 A CN109320539 A CN 109320539A
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- isoquinolin
- spiral shell
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- -1 isoquinolin indolinone derivative Chemical class 0.000 title claims abstract description 50
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- QEQVCPKISCKMOQ-UHFFFAOYSA-N 3h-benzo[f][1,2]benzoxazine Chemical class C1=CC=CC2=C(C=CNO3)C3=CC=C21 QEQVCPKISCKMOQ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000010189 synthetic method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Chemical group 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 50
- 239000010703 silicon Substances 0.000 claims description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 42
- 239000001301 oxygen Substances 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 36
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 35
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 125000005605 benzo group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 14
- VCYBVWFTGAZHGH-UHFFFAOYSA-N 1-methylindole-2,3-dione Chemical class C1=CC=C2N(C)C(=O)C(=O)C2=C1 VCYBVWFTGAZHGH-UHFFFAOYSA-N 0.000 claims description 13
- XEFCWBLINXJUIV-UHFFFAOYSA-N acetic acid;iodobenzene Chemical compound CC(O)=O.CC(O)=O.IC1=CC=CC=C1 XEFCWBLINXJUIV-UHFFFAOYSA-N 0.000 claims description 12
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 8
- YRXICXUINRGLJP-UHFFFAOYSA-N hydroxy(dimethyl)silicon Chemical compound C[Si](C)O YRXICXUINRGLJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- CAWBOJFIANSPRE-UHFFFAOYSA-N [I].C(C(=O)O)(=O)O Chemical compound [I].C(C(=O)O)(=O)O CAWBOJFIANSPRE-UHFFFAOYSA-N 0.000 claims description 2
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000004429 atom Chemical group 0.000 abstract description 3
- 238000006452 multicomponent reaction Methods 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- CGACGSHTSCXSSO-UHFFFAOYSA-N 2h-1,3-benzoxazine Chemical class C1=CC=C2C=NCOC2=C1 CGACGSHTSCXSSO-UHFFFAOYSA-N 0.000 description 9
- KGWNRZLPXLBMPS-UHFFFAOYSA-N 2h-1,3-oxazine Chemical class C1OC=CC=N1 KGWNRZLPXLBMPS-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010490 three component reaction Methods 0.000 description 3
- XRSLHTIRZNFPFF-UHFFFAOYSA-N 1,5-dimethylindole-2,3-dione Chemical compound CC1=CC=C2N(C)C(=O)C(=O)C2=C1 XRSLHTIRZNFPFF-UHFFFAOYSA-N 0.000 description 2
- NJOPQQPDPYWFFA-UHFFFAOYSA-N 5-chloro-1-methylindole-2,3-dione Chemical compound ClC1=CC=C2N(C)C(=O)C(=O)C2=C1 NJOPQQPDPYWFFA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OICIVPSURQBLRR-UHFFFAOYSA-N 1,3-dihydroindol-2-one quinoline Chemical class N1=CC=CC2=CC=CC=C21.C1=CC=C2NC(=O)CC2=C1 OICIVPSURQBLRR-UHFFFAOYSA-N 0.000 description 1
- JPTDPTOWOMFBRY-UHFFFAOYSA-N 1-methyl-5-nitroindole-2,3-dione Chemical compound [O-][N+](=O)C1=CC=C2N(C)C(=O)C(=O)C2=C1 JPTDPTOWOMFBRY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 150000005130 benzoxazines Chemical group 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IRFHMTUHTBSEBK-QGZVFWFLSA-N tert-butyl n-[(2s)-2-(2,5-difluorophenyl)-3-quinolin-3-ylpropyl]carbamate Chemical compound C1([C@H](CC=2C=C3C=CC=CC3=NC=2)CNC(=O)OC(C)(C)C)=CC(F)=CC=C1F IRFHMTUHTBSEBK-QGZVFWFLSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/20—Spiro-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to a kind of spiral shell benzoxazine and isoquinolin indolinone or spiral shell naphtho- oxazines and isoquinolin indolinone derivative and its synthetic method, the compound have the following structure: (1)With(2)
Description
Technical field
The present invention relates to a kind of spiral shell benzoxazine and isoquinolin indolinone or spiral shell naphtho- oxazines and isoquinolin indolinones
Derivative and its synthetic method.
Background technique
Compound containing spiral shell benzoxazine skeleton is widely used in making fire retardant, refractory material and important doctor
Medicine intermediate etc. wherein having had received widespread attention due to preferable photochromic properties, and is applied to store
The numerous areas such as equipment, optical switch, chemical sensitisation, optical mirror slip.
Multicomponent chemical reaction has the characteristics that easy to operate, resource utilization is high and high atom economy, is a kind of weigh
The organic chemical reactions wanted have a wide range of applications in new drug design and the synthesis of synthesis, combinatorial chemistry and natural products.It utilizes
The multi-component reaction that aryne participates in, synthesizing new complicated and diversified has multi-functional fragrant (miscellaneous) cycle compound, aggreggate utility
Increasingly significant.
Summary of the invention
One of the objects of the present invention is to provide a kind of spiral shell benzoxazine and isoquinolin indolinone or spiral shell naphtho- oxazines simultaneously
Isoquinolin indolinone derivative.
The second object of the present invention is to provide the synthetic method of the derivative.
The present invention is to form benzyne in a mild condition using benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen as aryne precursor
Or naphthalyne, three component reactions occur with N-methyl-isatin derivative and isoquinolin respectively, synthesis obtains spiral shell benzoxazine and isoquinoline
Quinoline indolinone or spiral shell naphtho- oxazines and isoquinolin indolinone derivative.Reaction process of the invention are as follows:
Bis- (two silicon of the oxygen cyclopentadienyls) 1 of benzo or two silicon substrate naphthalene 7 of oxygen are reacted with iodobenzene diacetate salt, trifluoromethanesulfonic acid, generate phenyl
[adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)] three fluosulfonic acid iodide 2 or phenyl [adjacent (hydroxyl dimethyl-silicon
Base) naphthalene] three fluosulfonic acid iodide 8.Under cesium fluoride (CsF) effect, benzyne intermediate 3 or naphthalyne intermediate 9 are generated,
Three component reactions occur with N-methyl-isatin derivative 4a-e and isoquinolin respectively, synthesis two silicon substrate spiral shell benzoxazine of oxygen is simultaneously different
Quinoline indolinone derivative 5b-e and three silicon substrate spiral shell benzoxazine of dioxy and isoquinolin indolinone derivative 6a, yield
For 39-77%；Or spiral shell naphtho- oxazines and isoquinolin indolinone derivative 10a-d, yield 25-55%.
According to above-mentioned reaction mechanism, the present invention adopts the following technical scheme:
A kind of spiral shell benzoxazine or naphtho- oxazines and isoquinolin indolinone derivative, it is characterised in that the compound has as follows
One of structure:
(1)With
(2)
Wherein R is methoxyl group, methyl, hydrogen, chlorine or nitro.
A method of preparing above-mentioned spiral shell benzoxazine or naphtho- oxazines and isoquinolin indolinone derivative, feature
It is that this method has following steps:
A. under the protection of inert nitrogen gas, trifluoromethanesulfonic acid is added to the dichloro of iodobenzene diacetate salt by ice-water bath condition
In dichloromethane, ice-water bath reacts 0.5~1 hour, reacts at room temperature 1~2 hour；The reaction solution is added under the conditions of ice-water bath
Into cooling benzo bis- (two silicon of oxygen cyclopentadienyls) or the dichloromethane solution of two silicon substrate naphthalene of oxygen, it is small to continue ice-water bath reaction 0.5~1
When, it reacts at room temperature 3~4 hours, is extracted with dichloromethane, washes, dry and revolve solvent, obtain phenyl [adjacent (hydroxyl dimethyl
Two silicon substrate fused phenyl of silicon substrate oxygen)] three fluosulfonic acid iodide or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodine
Compound, structural formula are as follows:Or；The oxalic acid iodine
The structural formula of benzene salt are as follows: PhI (OAc)2；
The structural formula of the benzo bis- (two silicon of oxygen cyclopentadienyls) are as follows:；
The structural formula of the two silicon substrate naphthalene of oxygen are as follows:；
B. under inert atmosphere protection, the phenyl obtained by step a [adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)] three
In the dichloromethane solution of fluosulfonic acid iodide or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide in batches
It is added in the dichloromethane solution of isoquinolin, N-methyl-isatin derivative and cesium fluoride, flows back 22~24 hours, mentioned through separation
It is pure, obtain two silicon substrate spiral shell benzoxazine of solid and three silicon substrate spiral shell benzoxazine of isoquinolin indolinone derivative 5b-e and dioxy
And simultaneously isoquinolin indolinone derivative 10a-d, structural formula are distinguished for isoquinolin indolinone derivative 6a or benzoxazine
Are as follows:
WithOr
The structural formula of the N-methyl-isatin derivative are as follows:, the structural formula of the isoquinolin are as follows:；The iodobenzene diacetate, trifluoromethanesulfonic acid, benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen, N-methyl-isatin
The molar ratio of derivative, isoquinolin, cesium fluoride (CsF) are as follows: 1.0~1.5: 2.5~3.0: 1.0~1.5: 0.5:0.5
~0.6:9.5~10.0.
The method of the present invention is using benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen as benzyne or naphthalyne precursor, at room temperature
Benzyne and naphthalyne are formed, three component reactions further occur with N-methyl-isatin derivative and isoquinolin, synthesizes spiral shell benzoxazine
And isoquinolin indolinone derivative or spiral shell naphtho- oxazines and isoquinolin indolone derivatives.The synthetic method has reaction condition
Mildly, the advantages that environmental-friendly, one kettle way.
It theoretically analyzes, this method experienced multi-component reaction, for building spiral shell benzoxazine and isoquinolin indolinone
Or simultaneously isoquinolin indolinone molecular skeleton provides synthesis thinking to spiral shell naphtho- oxazines, enriches the synthesis of organic heterocyclic molecule
Method.The method of the present invention is easy to operate, and reaction condition is mild, meets Atom economy requirement.
Specific embodiment
Embodiment one: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), the bis- (oxygen of benzo
Two silicon cyclopentadienyl) (1,1.0~1.5 eq), 5- methoxy-. N-methyl isatin (4a, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), fluorine
Change caesium (9.5~10.0 eq), resulting spiral shell benzoxazine and isoquinolin indolinone derivative: 1 '-methyl -5 '-methoxyl group -
Three silicon substrate -4b of 8,9- dioxyHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] 6,3 '--one of indoline -2 ' (6a) of isoquinolin -,
Yield 39%.The structure of the compound are as follows:
6a: molecular formula: C31H36N2O5Si3
Chinese name: 1 '-methyl -5 '-three silicon substrate -4b of methoxyl group -8,9- dioxyHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,
3-a] isoquinolin-the 6,3 '--one of indoline -2 '
English name: 1 '-Methyl-5 '-methoxy-8,9-dioxatrsilole-4bH-spiro[benzo[4,5][1,
3]oxazino[2,3-a]isoquinoline-6,3'-indolin]-2’-one
Molecular weight: 600.19
Fusing point: 93-95 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ0.09 (s, 3H), 0.10 (s, 3H), 0.11
(s, 3H), 0.23 (s, 3H), 0.39 (s, 3H), 0.47 (s, 3H), 3.29 (s, 3H), 3.66 (s,
3H), 5.80 (d, J = 7.5 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 6.73 (s, 1H), 6.78-
6.81 (m, 2H), 6.91 (d, J = 7.5 Hz, 1H), 7.12 (d, J = 7.5 Hz, 1H), 7.16-7.19
(m, 1H), 7.27-7.30 (m, 1H), 7.40 (s, 1H), 7.44 (d, J = 7.5 Hz, 1H), 7.51 (s,
1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 0.7, 1.5, 1.8, 1.9, 2.1, 26.4,
55.9, 80.2, 80.5, 100.7, 108.8, 111.6, 115.0, 123.5, 124.2, 125.0, 125.6,
126.0, 128.3, 129.1, 129.3, 131.5, 132.1, 132.4, 137.4, 139.7, 141.0, 146.9,
156.6, 176.0 ppm.
Embodiment two: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), bis- (two silicon of oxygen of benzo
Cyclopentadienyl) (1,1.0~1.5 eq), 5- methyl-N-methyl isatin (4b, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride
(9.5~10.0 eq), gained spiral shell benzoxazine and isoquinolin indolinone derivative are as follows: 1 ', 5 '-dimethyl -8,9- oxygen, two silicon
Base -4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] 6,3 '--one of indoline -2 ' (5b) of isoquinolin -, total yield 48%.It should
The structure of compound are as follows:
5b: molecular formula: C29H30N2O3Si2
Chinese name: 1 ', 5 '-dimethyl -8,9- oxygen, two silicon substrate -4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinoline
Quinoline-the 6,3 '--one of indoline -2 '
English name: 1 ', 5 '-Dimethyl-8,9-oxadisilole-4bH-spiro[benzo[4,5][1,3]oxazino
[2,3-a]isoquinoline-6,3'-indolin]-2’-one
Molecular weight: 510.18
Fusing point: 107-109 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 0.19 (s, 3H), 0.28 (s, 3H), 0.35
(s, 3H), 0.43 (s, 3H), 2.19 (s, 3H), 3.31 (s, 3H), 5.80 (d, J = 8.0 Hz, 1H),
6.78 (d, J = 8.0 Hz, 2H), 6.86 (d, J = 1.0 Hz, 1H), 6.96 (d, J = 7.5 Hz, 1H),
7.08-7.12 (m, 2H), 7.15-7.19 (m, 1H), 7.27-7.29 (m, 1H), 7.42 (d, J = 7.5 Hz,
1H), 7.47 (s, 1H), 7.49 (s, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 1.0, 1.1, 1.2, 1.3, 20.9, 26.5,
80.1, 80.3, 100.5, 108.2, 120.5, 124.1, 125.0, 125.6, 125.9, 127.1, 128.7,
129.05, 129.08, 129.2, 130.3, 131.4, 131.6, 133.3, 141.78, 141.84, 142.4,
148.8, 176.1 ppm.
Embodiment three: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), bis- (two silicon of oxygen of benzo
Cyclopentadienyl) (1,1.0~1.5 eq), N-methyl-isatin (4c, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5~
10.0 eq), gained spiral shell benzoxazine and isoquinolin indolinone derivative are as follows: 1 '-methyl -8,9- oxygen, two silicon substrate -4bHSpiral shell benzene
And [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,3 '-indoline -2 ' -one (5c), total yield 65%.The knot of the compound
Structure are as follows:
5c: molecular formula: C28H28N2O3Si2
Chinese name: 1 '-methyl -8,9- oxygen, two silicon substrate -4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,
The 3 '--one of indoline -2 '
English name: 1 '-Methyl-8,9-oxadisilole-4bH-spiro[benzo[4,5][1,3]oxazino[2,3-a]isoquinoline-6,3'-indolin]-2’-one
Molecular weight: 496.16
Fusing point: 147-149 oC
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.18 (s, 3H), 0.28 (s, 3H), 0.36
(s, 3H), 0.42 (s, 3H), 3.34 (s, 3H), 5.80 (d, J = 7.5 Hz, 1H), 6.77 (s, 1H),
6.89 (d, J = 7.5 Hz, 1H), 6.93-6.97 (m, 2H), 7.03-7.05 (m, 1H), 7.12 (d, J =
7.5 Hz, 1H), 7.16-7.19 (m, 1H), 7.27-7.31 (m, 2H), 7.44 (d, J = 7.5 Hz, 1H),
7.47 (s, 1H), 7.49 (s, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ0.9, 1.0, 1.1, 1.2, 26.4, 79.9,
80.3, 100.6, 108.4, 120.4, 123.6, 124.1, 124.9, 125.0, 126.0, 127.0, 128.6,
129.0, 129.3, 130.1, 131.49, 131.53, 141.8, 142.4, 144.2, 148.8, 176.1 ppm.
Example IV: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), bis- (two silicon of oxygen of benzo
Cyclopentadienyl) (1,1.0~1.5 eq), 5- chloro-n-methyl isatin (4c, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5
~10.0 eq), gained spiral shell benzoxazine and isoquinolin indolinone derivative are as follows: 1 '-methyl -5 '-two silicon substrate of chloro- 8,9- oxygen -
4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,3 '-indoline -2 ' -one (5d), total yield 70%.The change
Close the structure of object are as follows:
5d: molecular formula: C28H27ClN2O3Si2
Chinese name: 1 '-methyl -5 '-chloro- 8,9- oxygen, two silicon substrate -4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinoline
Quinoline-the 6,3 '--one of indoline -2 '
English name: 1 '-Methyl-5 '-chloro-8,9-oxadisilole-4bH-spiro[benzo[4,5][1,3]
oxazino[2,3-a]isoquinoline-6,3'-indolin]-2’-one
Molecular weight: 530.12
Fusing point: 173-175 oC
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 0.22 (s, 3H), 0.28 (s, 3H), 0.36
(s, 3H), 0.43 (s, 3H), 3.32 (s, 3H), 5.83 (d, J = 7.5 Hz, 1H), 6.75 (s, 1H),
6.82 (d, J = 8.0 Hz, 1H), 6.96 (d, J = 7.5 Hz, 1H), 7.01 (d, J = 2.5 Hz, 1H),
7.14 (d, J = 7.5 Hz, 1H), 7.17-7.20 (m, 1H), 7.28-7.31 (m, 2H), 7.40 (s, 1H),
7.42 (d, J = 7.5 Hz, 1H), 7.48 (s, 1H) ppm;
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 0.9, 1.0, 1.2, 1.3, 26.6, 79.8,
80.6, 100.8, 109.5, 120.8, 124.3, 124.6, 125.4, 126.1, 126.2, 128.5, 128.7,
128.9, 129.0, 129.4, 130.0, 131.5, 133.1, 142.2, 142.4, 142.8, 149.3, 175.7
ppm.
Embodiment five: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), bis- (two silicon of oxygen of benzo
Cyclopentadienyl) (1,1.0~1.5 eq), 5- nitro-N-methyl-isatin (4e, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride
(9.5~10.0 eq), gained spiral shell benzoxazine and isoquinolin indolinone derivative are as follows: 1 '-methyl -5 '-nitro -8,9- oxygen
Two silicon substrate -4bHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,3 '-indoline -2 ' -one (5e), total yield
77%.The structure of the compound are as follows:
5e: molecular formula: C28H27N3O5Si2
Chinese name: 1 '-methyl -5 '-two silicon substrate -4b of nitro -8,9- oxygenHSpiral shell benzo [4,5] [1,3] oxazines simultaneously [2,3-a] different
Quinoline-the 6,3 '--one of indoline -2 '
English name: 1 '-Methyl-5 '-nitro-8,9-oxadisilole-4bH-spiro[benzo[4,5][1,3]
oxazino[2,3-a]isoquinoline-6,3'-indolin]-2’-one
Molecular weight: 541.15
Fusing point: 259-261 oC
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 0.18 (s, 3H), 0.27 (s, 3H), 0.37
(s, 3H), 0.44 (s, 3H), 3.41 (s, 3H), 5.86 (d, J = 7.5 Hz, 1H), 6.70 (s, 1H),
6.99-7.00 (m, 2H), 7.15-7.21 (m, 2H), 7.29-7.32 (m, 1H), 7.34 (s, 1H), 7.40
(d, J = 7.5 Hz, 1H), 7.52 (s, 1H), 7.88 (d, J = 2.0 Hz, 1H), 8.27-8.29 (m,
1H) ppm;
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 0.91, 0.94, 1.2, 1.3, 26.9, 79.2,
80.9, 101.1, 108.4, 121.0, 121.1, 124.3, 124.5, 125.3, 126.1, 127.1, 128.4,
128.5, 128.9, 129.6, 131.5, 132.7, 142.4, 142.5, 144.0, 149.90, 149.94, 176.0
ppm.
Embodiment six: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen (8,
1.0~1.5 eq), 5- methoxy-. N-methyl isatin (4a, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5~
10.0 eq), resulting spiral shell benzoxazine and isoquinolin indolinone derivative: 1 '-methyl -5 '-methoxyl group -4bHSpiral shell naphtho-
[2', 3':4,5] [1,3] oxazines simultaneously [2,3-a] 6,3 '--one of indoline -2 ' (10a) of isoquinolin -, total yield 30%.The chemical combination
The structure of object are as follows:
10a: molecular formula: C29H22N2O3
Chinese name: 1 '-methyl -5 '-methoxyl group -4bHSpiral shell naphtho- [2', 3':4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin-
The 6,3 '--one of indoline -2 '
English name: 1 '-Methyl-5 '-methoxy-4bH-spiro[naphtho[2',3':4,5][1,3]oxazino[2,
3-a]isoquinoline-6,3'-indolin]-2'-one
Molecular weight: 446.16
Fusing point: 142-144 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 3.34 (s, 3H), 3.62 (s, 3H), 5.83
(d,J = 7.5 Hz, 1H), 6.62 (s, 1H), 6.84 (d, J = 1.0 Hz, 2H), 7.05 (d, J = 7.5
Hz, 1H), 7.14 (d, J = 7.5 Hz, 1H), 7.16-7.20 (m, 2H), 7.28-7.33 (m, 2H),
7.43-7.47 (m, 2H), 7.57 (d, J = 8.5 Hz, 1H), 7.64 (s, 1H), 7.68 (s, 1H), 7.79
(d, J = 8.0 Hz, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 26.5, 55.7, 80.4, 80.9, 100.6,
109.1, 111.5, 114.5, 115.3, 124.2, 124.8, 124.9, 126.0, 126.3, 126.88,
126.91, 127.7, 129.1, 129.28, 129.33, 129.8, 131.6, 133.1, 133.3, 137.4,
139.8, 156.7, 176.1 ppm.
Embodiment seven: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen (8,
1.0~1.5 eq), 5- methyl-N-methyl isatin (4b, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5~
10.0 eq), resulting spiral shell benzoxazine and isoquinolin indolinone derivative: 1 ', 5 '-dimethyl -4bHSpiral shell naphtho- [2',
3':4,5] [1,3] oxazines simultaneously [2,3-a] 6,3 '--one of indoline -2 ' (10b) of isoquinolin -, total yield 25%.The compound
Structure are as follows:
10b: molecular formula: C29H22N2O2
Chinese name: 1 ', 5 '-dimethyl -4bHSpiral shell naphtho- [2', 3':4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,3 ' -
The -one of indoline -2 '.
English name: 1 ', 5 '-Dimethyl-4bH-spiro[naphtho[2',3':4,5][1,3]oxazino[2,3-a]isoquinoline-6,3'-indolin]-2'-one
Molecular weight: 430.17
Fusing point: 201-204 DEG C
Appearance: yellow powder
Outer nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 2.15 (s, 3H), 3.34 (s, 3H),
5.84 (d,J = 7.5 Hz, 1H), 6.81-6.84 (m, 2H), 7.05 (d, J = 7.5 Hz, 1H), 7.10-
7.11 (m, 1H), 7.14 (d, J = 8.0 Hz, 1H),7.16-7.20 (m, 2H), 7.28-7.34 (m, 2H),
7.44-7.47 (m, 2H), 7.58 (d, J = 8.5 Hz, 1H), 7.63 (s, 1H), 7.69 (s, 1H), 7.80
(d, J = 8.5 Hz, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 20.9, 26.4, 80.2, 80.9, 100.6,
108.2, 114.5, 124.2, 124.8, 124.9, 125.7, 126.0, 126.3, 126.4, 126.8, 126.9,
127.7, 129.1, 129.30, 129.33, 129.8, 130.4, 131.6, 132.1, 133.3, 133.4,
141.7, 176.2 ppm.
Embodiment eight: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen (8,
1.0~1.5 eq), N-methyl-isatin (4c, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5~10.0 eq),
Resulting spiral shell benzoxazine and isoquinolin indolinone derivative: 1 '-methyl -4bHSpiral shell naphtho- [2', 3':4,5] [1,3] oxazines
And [2,3-a] 6,3 '--one of indoline -2 ' (10c) of isoquinolin -, total yield 46%.The structure of the compound are as follows:
10c: molecular formula: C28H20N2O2
Chinese name: 1 '-methyl -4bHSpiral shell naphtho- [2', 3':4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,3 '-indoles
The -one of quinoline -2 '.
English name: 1 '-Methyl-4bH-spiro[naphtho[2',3':4,5][1,3]oxazino[2,3-a]
isoquinoline-6,3'-indolin]-2'-
one
Molecular weight: 416.15
Fusing point: 179-181 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 3.36 (s, 3H), 5.84 (d, J = 7.5 Hz,
1H), 6.92-6.96 (m, 2H), 7.02-7.05 (m, 2H), 7.14-7.17 (m, 2H), 7.18-7.21 (m,
1H), 7.29-7.33 (m, 3H), 7.43-7.48 (m, 2H), 7.57 (d, J = 8.0 Hz, 1H), 7.63 (s,
1H), 7.69 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 26.4, 80.0, 80.9, 100.6, 108.5,
114.6,123.7,124.2,124.8,124.9,125.0,126.0,126.3,126.2,126.9,127.7,
129.0, 129.30, 129.34, 129.8, 130.1, 131.6, 132.1, 133.3, 139.8, 144.1, 176.2
ppm.
Embodiment nine: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen (8,
1.0~1.5 eq), 5- chloro-n-methyl isatin (4d, 0.5 eq), isoquinolin (0.5 ~ 0.6 eq), cesium fluoride (9.5~10.0
Eq), resulting spiral shell benzoxazine and isoquinolin indolinone derivative: 1 '-methyl -5 '-chloro- 4bHSpiral shell naphtho- [2', 3':4,
5] [1,3] oxazines simultaneously [2,3-a] 6,3 '--one of indoline -2 ' (10d) of isoquinolin -, total yield 55%.The structure of the compound are as follows:
10d: molecular formula: C28H19ClN2O2
Chinese name: 1 '-methyl -5 '-chloro- 4bHSpiral shell naphtho- [2', 3':4,5] [1,3] oxazines simultaneously [2,3-a] isoquinolin -6,
The 3 '--one of indoline -2 '
English name: 1 '-Methyl-5 '-chloro-4bH-spiro[naphtho[2',3':4,5][1,3]oxazino[2,
3-a]isoquinoline-6,3'-indolin]-2'-one
Molecular weight: 450.11
Fusing point: 203-205 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 3.35 (s, 3H), 5.86 (d, J = 7.5 Hz,
1H), 6.85 (d, J = 8.0 Hz, 1H), 7.00 (d, J =1.5 Hz, 1H), 7.05 (d, J = 7.5 Hz,
1H), 7.16-7.19 (m, 2H), 7.21 (d, J = 7.5 Hz, 1H), 7.27-7.36 (m, 3H), 7.45-
7.47 (m, 2H), 7.58-7.60 (m, 2H), 7.70 (s, 1H), 7.81 (d, J = 8.5 Hz, 1H) ppm.
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 26.5, 79.9, 81.1, 100.8, 109.5,
114.9, 124.3, 124.5, 125.1, 125.4, 125.5, 126.05, 126.11, 127.0, 127.1,
127.7, 129.0, 129.3, 129.5, 129.8, 130.0, 131.5, 133.4, 133.7, 139.7, 142.6,
175.8 ppm.。
Claims (2)
1. a kind of spiral shell benzoxazine or naphtho- oxazines and isoquinolin indolinone derivative, it is characterised in that the compound has such as
One of flowering structure:
(1)With
(2)
Wherein R is methoxyl group, methyl, hydrogen, chlorine or nitro.
2. a kind of spiral shell benzoxazine or naphtho- oxazines according to claim 1 and isoquinolin indolinone derivative of preparing
Method, it is characterised in that this method has following steps:
A. under the protection of inert nitrogen gas, trifluoromethanesulfonic acid is added to the dichloro of iodobenzene diacetate salt by ice-water bath condition
In dichloromethane, ice-water bath reacts 0.5~1 hour, reacts at room temperature 1~2 hour；The reaction solution is added under the conditions of ice-water bath
Into cooling benzo bis- (two silicon of oxygen cyclopentadienyls) or the dichloromethane solution of two silicon substrate naphthalene of oxygen, it is small to continue ice-water bath reaction 0.5~1
When, it reacts at room temperature 3~4 hours, is extracted with dichloromethane, washes, dry and revolve solvent, obtain phenyl [adjacent (hydroxyl dimethyl
Two silicon substrate fused phenyl of silicon substrate oxygen)] three fluosulfonic acid iodide or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodine
Compound, structural formula are as follows:Or；The oxalic acid iodine
The structural formula of benzene salt are as follows: PhI (OAc)2；
The structural formula of the benzo bis- (two silicon of oxygen cyclopentadienyls) are as follows:；
The structural formula of the two silicon substrate naphthalene of oxygen are as follows:；
B. under inert atmosphere protection, the phenyl obtained by step a [adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)] three
In the dichloromethane solution of fluosulfonic acid iodide or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide in batches
It is added in the dichloromethane solution of isoquinolin, N-methyl-isatin derivative and cesium fluoride, flows back 22~24 hours, mentioned through separation
It is pure, obtain two silicon substrate spiral shell benzoxazine of solid and three silicon substrate spiral shell benzoxazine of isoquinolin indolinone derivative 5b-e and dioxy
And simultaneously isoquinolin indolinone derivative 10a-d, structural formula are distinguished for isoquinolin indolinone derivative 6a or benzoxazine
Are as follows:
WithOr
The structural formula of the N-methyl-isatin derivative are as follows:, the structural formula of the isoquinolin are as follows:；The iodobenzene diacetate, trifluoromethanesulfonic acid, benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen, N-methyl-isatin
The molar ratio of derivative, isoquinolin, cesium fluoride (CsF) are as follows: 1.0~1.5: 2.5~3.0: 1.0~1.5: 0.5:0.5
~0.6:9.5~10.0.
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|---|---|---|---|---|
| WO2014184808A1 (en) * | 2013-05-15 | 2014-11-20 | Council Of Scientific And Industrial Research | Spiro-oxazines, indolinones and preparation thereof |
| CN104592290A (en) * | 2015-01-23 | 2015-05-06 | 上海大学 | Phenanthridine derivatives and synthetic methods thereof |
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| CN107082761A (en) * | 2017-04-17 | 2017-08-22 | 上海大学 | Phenanthridone or benzo phenanthridines ketone derivatives and its synthetic method |
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2018
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| WO2014184808A1 (en) * | 2013-05-15 | 2014-11-20 | Council Of Scientific And Industrial Research | Spiro-oxazines, indolinones and preparation thereof |
| CN104592290A (en) * | 2015-01-23 | 2015-05-06 | 上海大学 | Phenanthridine derivatives and synthetic methods thereof |
| CN106432316A (en) * | 2016-09-24 | 2017-02-22 | 上海大学 | Indole piperazoisoindole or benzoindole piperazoisoindole derivative and synthesis method thereof |
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