CN110028516A - A kind of synthetic method for the spiro-pyrans class compound preparing the substitution of bromo alkoxy - Google Patents
A kind of synthetic method for the spiro-pyrans class compound preparing the substitution of bromo alkoxy Download PDFInfo
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- CN110028516A CN110028516A CN201910463040.2A CN201910463040A CN110028516A CN 110028516 A CN110028516 A CN 110028516A CN 201910463040 A CN201910463040 A CN 201910463040A CN 110028516 A CN110028516 A CN 110028516A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000006467 substitution reaction Methods 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- -1 benzazolyl compounds Chemical class 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 230000029936 alkylation Effects 0.000 abstract description 3
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- JNXWKNHPQJCSHO-UHFFFAOYSA-N 2,3,3-trimethylindol-5-ol Chemical class C1=C(O)C=C2C(C)(C)C(C)=NC2=C1 JNXWKNHPQJCSHO-UHFFFAOYSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 241001141101 Nitrospirales Species 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OKISVAYIVBWMDU-UHFFFAOYSA-N 2-methyl-3h-indole Chemical class C1=CC=C2CC(C)=NC2=C1 OKISVAYIVBWMDU-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000002894 chemical waste Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WPVXOOFOWPVFTK-UHFFFAOYSA-N (2-formylphenyl) nitrate Chemical compound [O-][N+](=O)OC1=CC=CC=C1C=O WPVXOOFOWPVFTK-UHFFFAOYSA-N 0.000 description 1
- STBMZSJLFYGOJU-UHFFFAOYSA-N 1,1-dibromooctane Chemical compound CCCCCCCC(Br)Br STBMZSJLFYGOJU-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a kind of synthetic methods of spiro-pyrans class compound for preparing the substitution of bromo alkoxy, belong to organic synthesis field.For the present invention with 5- hydroxyl -2,3,3- trimethyl -3H- indoles is starting material, obtains the spiro-pyrans class compound of 5 '-bromo alkoxies substitution by the alkylation of phenolic hydroxyl group bromo and spiro-pyrans synthesis two-step reaction.The process route is simple, and reaction process does not need anhydrous and oxygen-free operation, effectively prevents the hydrolytic side reactions of spiro-pyrans during such previous compound synthesis, has many advantages, such as that combined coefficient is high, comprehensive yied is high.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of spiro-pyrans class compound for preparing the substitution of bromo alkoxy
Synthetic method.
Background technique
Photosensitive molecular can realize structural isomerism under light stimulation, and changing with physics and chemical property simultaneously
Become.Photosensitive molecular can be applied as molecular switch in biomedicine field and Material Field.
Spiro-pyrans class compound is most commonly seen one of light-sensitive compound, and under different illumination conditions, having can backlight
The property of mutagens color.Under ultraviolet light, spiropyran compounds are changed into open loop situations by closed loop states.In radiation of visible light
Under, the reversible change of above-mentioned variation occurs.Spiropyran compounds are important dye molecule.
In numerous spiropyran compounds, the 6- nitro spiro-pyrans that 5 '-bromo alkoxies replace is most widely used
One of molecule.Such compound can more easily introduce other structures group in alkyl end, in scientific research and work
Industry production field has huge demand.Up to the present, the synthesis of such compound generally first constructs spiro-pyrans knot for cut-off
Then structure unit is alkylated in 5 '-positions, combined coefficient is relatively low.
In the above method, the building of spiro-pyrans is completed by two-step reaction first, then is alkylated in 5 '-positions anti-
Answer (The Journal of Organic Chemistry, 2007,72,595-605).Under alkaline condition due to spiro-pyrans
Hydrolytic side reactions (Chemical Communications, 2009,287-288), the 6- nitro spiral shell for causing 5 '-alkoxies to replace
The generated time length of pyran compounds, low yield.In addition to this, entire synthesis step includes three-step reaction, is generated more
Chemical waste.
Summary of the invention
The synthesis step of the 6- nitro spiro-pyrans class compound replaced for 5 '-bromo alkoxies is more and combined coefficient is low
The problem of, the present invention provides a kind of improved synthetic methods for preparing such compound.
Technical scheme is as follows:
The 6- nitro spiro-pyrans class compound that 5 ' synthesized in the present invention-bromo alkoxy replaces, has the following structure formula:
A kind of synthetic method for the spiro-pyrans class compound preparing the substitution of bromo alkoxy comprising following steps:
Step 1: 5- hydroxyl -2,3 that molar ratio is 1:1:1.5,3- trimethyl -3H- indoles, potassium carbonate and dibromo are weighed
It is dissolved in acetone for alkane, which is heated to reflux 24 hours under agitation, and reaction system is cooled to room temperature, and passes through
It is filtered, washed and is purified with silica gel column chromatography, the benzazolyl compounds of bromo alkoxy substitution are prepared；
Step 2: weigh benzazolyl compounds that the bromo alkoxy that is prepared in step 1 replaces and iodomethane (mole
Than being dissolved in solvent A for 1:2), which is heated to reflux 12 hours under agitation, and reaction system is cooled to room
Temperature；Weighing organic base B respectively, (organic base B is catalyst, mole for the benzazolyl compounds that organic base B and bromo alkoxy replace
Than for 1:1) and 5- nitrosalicylaldehyde (molar ratio for the benzazolyl compounds that 5- nitrosalicylaldehyde and bromo alkoxy replace is 1:1)
It is added in above-mentioned reaction system, which is stirred to react 5 minutes at room temperature, then it is concentrated through vacuum distillation,
Yellow solid is prepared through silica gel column chromatography.
Solvent A is any one of methanol, ethyl alcohol, acetonitrile or tetrahydrofuran or its mixed solvent, and organic base B is piperazine
Any one of pyridine, triethylamine, dimethylamine or 4-dimethylaminopyridine.
Experimental program of the invention is compared to the synthetic method of report early period, has the following obvious advantages:
The synthesis of such compound is reduced to two-step reaction by three-step reaction for the first time, does not need anhydrous and oxygen-free operation, it is real
Operation is tested to greatly simplify；
In reported synthetic route, need first to prepare spiropyran compounds, then carry out the alkylation of phenolic hydroxyl group, so that
The spiro-pyrans of synthesis occurs hydrolytic side reactions and yield is caused to reduce, and the alkylation of phenolic hydroxyl group has been placed on synthesis by route of the present invention
Before spiro-pyrans, the hydrolysis of spiro-pyrans is effectively prevented, so that the comprehensive yied of entire synthesis process greatly improves；
Two-step method synthesis reduces chemical waste caused by last handling process in synthesis process.
Specific embodiment
Technical solution in order to preferably explain the present invention embodies the spiro-pyrans that the present invention replaces in synthesis of bromic alkane oxygroup
Advantage on class compound is further explained explanation by embodiment below:
Embodiment 1:5 '-(2- bromine oxethyl) -1', 3', 3'- trimethyl -6- nitro spiral shell [chromene -2,2'- indoles
Quinoline]
The flask of a 50mL is taken, reflux condensate device is installed, 2.0g (11.41mmol) 5- hydroxyl -2,3,3- tri- is added
Methyl -3H- indoles, 1577mg (11.41mmol) potassium carbonate, 1.48mL (17.12mmol) 1,2- Bromofume and 20mL
Acetone is heated to reflux 24 hours, reaction system is cooled to room temperature, and filters, and washing is spin-dried for solvent, with silica gel column chromatography (elution
Agent is petrol ether/ethyl acetate) to purification of products, -2,3,3- trimethyl -3H- indoles 837mg of 5- (2- bromine oxethyl) is obtained,
Yield 26%；Weigh 800mg (2.84 mmol) 5- (2- bromine oxethyl) -2,3,3- trimethyl -3H- indoles and 0.35ml
(5.68mmol) iodomethane is dissolved in 20mL methanol, which is heated to reflux 12 hours under agitation, will be reacted
System is cooled to room temperature；0.28mL (2.84 mmol) piperidines and 475mg (2.84mmol) 5- nitre are sequentially added into above-mentioned system
Base salicylide is further continued for reaction 5 minutes, solvent is spin-dried for, with silica gel column chromatography (eluant, eluent is petrol ether/ethyl acetate) to product
Purification, obtains yellow solid 784mg, yield 62%.
1H NMR(400MHz,CDCl3) δ 1.19 (s, 3H), 1.28 (s, 3H), 2.70 (s, 3H), 3.42 (t, J=6.8Hz,
0.62H), 3.64 (t, J=6.4Hz, 1.38H), (SPCH2:MCCH2=31:69), 4.21-4,29 (m, 2H), 5.85 (d, J=
10.4Hz, 1H), 6.46 (d, J=8Hz, 1H), 6.73-6.78 (m, 3H), 6.92 (d, J=9.6Hz, 1H), 8.00-8.02
(m,2H).
Embodiment 2:5 '-(3- bromine propoxyl group) -1', 3', 3'- trimethyl -6- nitro spiral shell [chromene -2,2'- indoles
Quinoline]
The flask of a 50mL is taken, reflux condensate device is installed, 2.0g (11.41mmol) 5- hydroxyl -2,3,3- tri- is added
Methyl -3H- indoles, 1577mg (11.41mmol) potassium carbonate, 1.74mL (17.12mmol) 1,3- dibromopropane and 20mL
Acetone is heated to reflux 24 hours, reaction system is cooled to room temperature, and filters, and washing is spin-dried for solvent, with silica gel column chromatography (elution
Agent is petrol ether/ethyl acetate) to purification of products, -2,3,3- trimethyl -3H- indoles 2447mg of 5- (3- bromine propoxyl group) is obtained,
Yield 76%；Weigh -2,3,3- trimethyl -3H- indoles of 2.0g (7.14 mmol) 5- (3- bromine propoxyl group) and 0.89ml
(14.28mmol) iodomethane is dissolved in 20mL ethyl alcohol, which is heated to reflux 12 hours under agitation, will be reacted
System is cooled to room temperature；1.0mL (7.14mmol) triethylamine and 1193mg (7.14mmol) 5- are sequentially added into above-mentioned system
Nitrosalicylaldehyde is further continued for reaction 5 minutes, solvent is spin-dried for, with silica gel column chromatography (eluant, eluent is petrol ether/ethyl acetate) to production
Object purification, obtains yellow solid 1968mg, yield 60%.
1H NMR(500MHz,CDCl3)δ1.20(s,3H),1.29(s,3H),2.25-2.34(m,2H),2.70(s,3H),
3.40 (t, J=6.5Hz, 1.45H), 3.63 (t, J=6.5Hz, 0.45H), (SPCH2:MCCH2=29:11), 4.02 (t, J=
6.0Hz, 1.45H), 4.08 (t, J=6.0Hz, 0.45H), (SPCH2:MCCH2=29:11), 5.86 (d, J=10.5Hz, 1H),
6.45-6.47 (m, 1H), 6.74-6.78 (m, 3H), 6.92 (d, J=10.5Hz, 1H), 8.00-8.02 (m, 2H)
Embodiment 3:5 '-(4- bromine butoxy) -1', 3', 3'- trimethyl -6- nitro spiral shell [chromene -2,2'- indoles
Quinoline]
The flask of a 50mL is taken, reflux condensate device is installed, 2.0g (11.41mmol) 5- hydroxyl -2,3,3- tri- is added
Methyl -3H- indoles, 1577mg (11.41mmol) potassium carbonate, 2.04mL (17.12mmol) Isosorbide-5-Nitrae-dibromobutane and 20mL
Acetone is heated to reflux 24 hours, reaction system is cooled to room temperature, and filters, and washing is spin-dried for solvent, with silica gel column chromatography (elution
Agent is petrol ether/ethyl acetate) to purification of products, -2,3,3- trimethyl -3H- indoles 3186mg of 5- (4- bromine butoxy) is obtained,
Yield 90%；Weigh -2,3,3- trimethyl -3H- indoles of 2.0g (6.45 mmol) 5- (4- bromine butoxy) and 0.80ml
(12.90mmol) iodomethane is dissolved in 20mL acetonitrile, which is heated to reflux 12 hours under agitation, will be reacted
System is cooled to room temperature；3.2mL (6.45mmol) 2mol/L dimethylamine and 1078mg are sequentially added into above-mentioned system
(6.45mmol) 5- nitrosalicylaldehyde, be further continued for reaction 5 minutes, be spin-dried for solvent, with silica gel column chromatography (eluant, eluent be petroleum ether/
Ethyl acetate) to purification of products, obtain yellow solid 1985mg, yield 65%.
1H NMR(500MHz,CDCl3)δ1.20(s,3H),1.28(s,3H),1.87-1.97(m,2H),2.03-2.12
(m, 2H), 2.69 (s, 3H), 3.28 (t, J=7.0Hz, 1H), 3.51 (t, J=5.6Hz, 1H), 3.95-3.99 (m, 2H),
5.86 (d, J=10.5Hz, 1H), 6.46 (d, J=8.0Hz, 1H), 6.71-6.73 (m, 2H), 6.77 (d, J=9.0Hz,
1H), 6.92 (d, J=10.5Hz, 1H), 8.00-8.02 (m, 2H)
Embodiment 4:5 '-(8- bromine octyloxy) -1', 3', 3'- trimethyl -6- nitro spiral shell [chromene -2,2'- indoles
Quinoline]
The flask of a 50mL is taken, reflux condensate device is installed, 2.0g (11.41mmol) 5- hydroxyl -2,3,3- tri- is added
Methyl -3H- indoles, 1577mg (11.41mmol) potassium carbonate, bis- bromooctane of 3.15mL (17.12mmol) 1,8- and 20mL
Acetone is heated to reflux 24 hours, reaction system is cooled to room temperature, and filters, and washing is spin-dried for solvent, with silica gel column chromatography (elution
Agent is petrol ether/ethyl acetate) to purification of products, -2,3,3- trimethyl -3H- indoles 3469mg of 5- (8- bromine octyloxy) is obtained,
Yield 83%；Weigh -2,3,3- trimethyl -3H- indoles of 2.0g (5.46 mmol) 5- (8- bromine octyloxy) and 0.68ml
(10.92mmol) iodomethane is dissolved in 20mL tetrahydrofuran, which is heated to reflux 12 hours under agitation, will
Reaction system is cooled to room temperature；667mg (5.46 mmol) 4-dimethylaminopyridine and 912mg are sequentially added into above-mentioned system
(5.46mmol) 5- nitrosalicylaldehyde, be further continued for reaction 5 minutes, be spin-dried for solvent, with silica gel column chromatography (eluant, eluent be petroleum ether/
Ethyl acetate) to purification of products, obtain yellow solid 2081mg, yield 72%.
1H NMR(400MHz,CDCl3)δ1.19(s,3H),1.28(s,3H),1.38-1.48(m,8H),1.75-1.91
(m, 4H), 2.69 (s, 3H), 3.20 (t, J=6.8Hz, 1.15H), 3.42 (t, J=6.8Hz, 0.85H), (SPCH2:MCCH2=
23:17), 3.93 (t, J=6.4Hz, 2H), 5.85 (d, J=10.4Hz, 1H), 6.45 (d, J=8.0Hz, 1H), 6.71-6.78
(m, 3H), 6.91 (d, J=10.4Hz, 1H), 8.00-8.02 (m, 2H).
Claims (2)
1. a kind of synthetic method for the spiro-pyrans class compound (its structural formula is shown in formula I) for preparing the substitution of bromo alkoxy:
It is characterized by: it the following steps are included:
Step 1: 5- hydroxyl -2,3 that molar ratio is 1:1:1.5,3- trimethyl -3H- indoles, potassium carbonate and dibromoalkane are weighed
It is dissolved in acetone, which is heated to reflux 24 hours under agitation, and reaction system is cooled to room temperature, and passes through
Filter, washing and silica gel column chromatography purifying, are prepared the benzazolyl compounds of bromo alkoxy substitution；
Step 2: weighing benzazolyl compounds that the bromo alkoxy that is prepared in step 1 replaces and iodomethane, (molar ratio is
It 1:2) is dissolved in solvent A, which is heated to reflux 12 hours under agitation, and reaction system is cooled to room temperature；
Weighing organic base B respectively, (organic base B is catalyst, and the molar ratio for the benzazolyl compounds that organic base B and bromo alkoxy replace is
1:1) it is added with 5- nitrosalicylaldehyde (molar ratio for the benzazolyl compounds that 5- nitrosalicylaldehyde and bromo alkoxy replace is 1:1)
Into above-mentioned reaction system, which is stirred to react 5 minutes at room temperature, is then concentrated through vacuum distillation, through silicon
Yellow solid is prepared in plastic column chromatography.
2. a kind of synthetic method of spiro-pyrans class compound for preparing the substitution of bromo alkoxy according to claim 1,
Be characterized in that: solvent A is any one of methanol, ethyl alcohol, acetonitrile or tetrahydrofuran or its mixed solvent, and organic base B is piperazine
Any one of pyridine, triethylamine, dimethylamine or 4-dimethylaminopyridine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606915A (en) * | 2020-07-17 | 2020-09-01 | 浙大宁波理工学院 | Preparation method of spiropyran photochromic material |
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2019
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Non-Patent Citations (2)
| Title |
|---|
| MASSIMILIANO TOMASULO，等: "Synthesis and Properties of Benzophenone-Spiropyran and Naphthalene-Spiropyran Conjugates", 《J.ORG.CHEM.》 * |
| 薛永强: "《现代有机合成方法与技术》", 31 May 2003 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606915A (en) * | 2020-07-17 | 2020-09-01 | 浙大宁波理工学院 | Preparation method of spiropyran photochromic material |
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Application publication date: 20190719 |