CN108822129A - A kind of isopropyl alkyl spirooxazine photochromic compound and its synthetic method - Google Patents
A kind of isopropyl alkyl spirooxazine photochromic compound and its synthetic method Download PDFInfo
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- CN108822129A CN108822129A CN201810494506.0A CN201810494506A CN108822129A CN 108822129 A CN108822129 A CN 108822129A CN 201810494506 A CN201810494506 A CN 201810494506A CN 108822129 A CN108822129 A CN 108822129A
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- isopropyl
- trimethyl
- indoles
- spirooxazine
- photochromic compound
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- 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
- C07D498/02—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 two hetero rings
- C07D498/10—Spiro-condensed systems
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Abstract
The invention discloses a kind of isopropyl alkyl spirooxazine photochromic compound and its synthetic method, the chemical name of the compound is N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine, and structural formula is：Isopropyl alkyl spirooxazine photochromic compound provided by the invention and its synthetic method, simple with preparation process, aftertreatment technology is easy, and product stability is good, as the photochromic material haveing excellent performance, the iterative cycles number of the spirooxazine reacted can reach 3*105More than, it is allowed to step an important step on paractical research.
Description
Technical field
The present invention relates to photochromic material preparation technical field, specially a kind of isopropyl alkyl spirooxazine photochromicization
Close object and its synthetic method.
Background technique
Photochromic material is the material that molecule contains photochromic functionalities, and the discoloration of this kind of material comes from
The photochromic group contained in molecule.Spirooxazine class photochromic material is one to grow up on the basis of spiro-pyrans
Class photochromic compound.Compared with spiro-pyrans, it has preferable light sensitivity and fatigue resistance, and application prospect is extensive.At present
This kind of compound of research is more, but without the spirooxazine class photochromic compound of isopropyl alkane substitution.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of photochromic chemical combination of isopropyl alkyl spirooxazine
Object and its synthetic method.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of isopropyl alkyl spirooxazine photochromic compound, its chemical name is N isopropyl [2,3,3- trimethyl -3H-
Indoles] spirooxazine, structural formula is：
A kind of synthetic method of isopropyl alkyl spirooxazine photochromic compound, includes the following steps：
Step 1, the synthesis of 2,3,3- trimethyl -3H- indoles：Using methyl isopropyl ketone and phenylhydrazine as reactant, through returning
Stream reaction obtains crude hydrazone, by resulting hydrazone and strong sulfuric acid response, obtains 2,3,3- trimethyl -3H- indoles；Reaction equation is such as
Under:
Step 2, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] iodide：To take Iso-Propyl iodide and step
One 2,3,3- obtained trimethyl -3H- indoles obtain N isopropyl [2,3,3- trimethyl -3H- through back flow reaction for reactant
Indoles] iodide；Reaction equation is as follows：
Step 3, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] indoline：The N isopropyl that step 2 is obtained
Iodide are dissolved in dehydrated alcohol base [2,3,3- trimethyl -3H- indoles], and triethylamine is added dropwise, and oil bath reacts to obtain N isopropyl
Base -2,3,3- trimethyl -3H indoline；Reaction equation is as follows：
Step 4, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine：By 1-Nitroso-2-naphthol plus
It is dissolved in dehydrated alcohol under heat, the orange-red solution of 1-Nitroso-2-naphthol is obtained by filtration, by above-mentioned orange-red solution and step 3
Obtained product obtains dark brown solid product through back flow reaction；Reaction equation is as follows：
The step 1 is specially：
It will be added in the phenylhydrazine being newly evaporated under reduced pressure by air-distillation methyl isopropyl ketone, this mixed liquor is under stiring
In 100 DEG C of back flow reactions, crude hydrazone is obtained；Obtained hydrazone is reacted in oil bath with the concentrated sulfuric acid, by vacuum distillation, instead
It should finish and be neutralized to alkalinity with NaOH, solution generates lamination；Water phase and organic phase, organic phase warp are separated with separatory funnel again
Air-distillation removes solvent, then is evaporated under reduced pressure, and collects 126 DEG C, the fraction of 2000Pa, products therefrom is pale yellow oily liquid.
The step 2 is specially：
It takes Iso-Propyl iodide and is mixed with 2,3, the 3- trimethyl -3H- indoles newly distilled, the back flow reaction 3 in 110 DEG C of oil bath
Hour, it is filtered under diminished pressure after cooling and collects solid crude product；It grinds after drying, is repeatedly washed with ethyl alcohol；Ethyl acetate is used after drying
It washs again, obtains clear crystal.
The step 3 is specially：
It takes N isopropyl [2,3,3- trimethyl -3H- indoles] iodide to be dissolved in dehydrated alcohol, is added dropwise three into this solution
Ethamine, and reacted 30 minutes at 90 DEG C of oil bath, obtain dark red solution.
The step 4 is specially：
1-Nitroso-2-naphthol is heated down and is dissolved in dehydrated alcohol, and active carbon is added, is boiled 10 minutes, after filtering
The transparent salmon solution of 1-Nitroso-2-naphthol is obtained, N isopropyl [2,3, the 3- trimethyls-for then obtaining step 3
3H- indoles] iodide are added in this reaction, continue back flow reaction 3-4 hour, and it is cooling after reaction, it is dry, it recrystallizes, obtains black
Brown solid product N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine.
In the step 4, the mixed solution of obtained brown solid product ethyl alcohol and acetone dissolves, then after recrystallizing
Obtain dark brown solid.
In the mixed solution of the ethyl alcohol and acetone, the volume ratio of ethyl alcohol and acetone is 1：1.
Beneficial effect：Isopropyl alkyl spirooxazine photochromic compound provided by the invention and its synthetic method have system
Standby simple process, aftertreatment technology are easy, and product stability is good, as the photochromic material haveing excellent performance, reacts
The iterative cycles number of spirooxazine can reach 3*105More than, it is allowed to step an important step on paractical research.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy for the product that embodiment obtains.
Specific embodiment
Below with reference to embodiment, the present invention will be further explained.
Embodiment
The preparation method of the present embodiment includes the following steps：
(1) synthesis of 2,3,3- trimethyl -3H- indoles
Experimentation and phenomenon：0.25mol methyl isopropyl ketone Jing Guo air-distillation is slowly added into new decompression
In the 0.25mol phenylhydrazine of distillation, for solution in orange colour and with exothermic phenomenon, this mixed liquor is anti-in 100 DEG C of reflux under stiring
It answers, obtains crude hydrazone；80mL dehydrated alcohol is added and makees solvent, catalyst concentrated sulfuric acid solution 15mL, oil are instilled within half an hour
It bathes 80 DEG C to react 3 hours, solution becomes orange red from yellow in reaction process, and end of reaction is neutralized to alkalinity, solution with NaOH
Generation lamination, upper layer crocus, lower layer are colourless.It is extracted with anhydrous ether, discards water phase, organic phase is dry with anhydrous magnesium sulfate
It is dry.After drying, it is filtered under diminished pressure with frosted funnel (sand core funnel) and stays ether layer.Ether (later period decompression) is evaporated off in normal pressure, then depressurizes steaming
Solution is evaporated, collects the fraction of 98-102 DEG C/15mmHg, products therefrom is pale yellow oily liquid, this liquid is indoles, yield
It is 72%.Reaction equation is as follows：
(2) synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] iodide
It takes the Iso-Propyl iodide of 0.158mol and 2,3,3- trimethyl -3H- indoles that 0.158mol newly distills mixes, in oil
It back flow reaction 3 hours in 110 DEG C of bath, is filtered under diminished pressure after cooling and collects solid crude product, solution is red.It grinds, uses after drying
Ethyl alcohol repeatedly washs, and product is white.It is washed again after drying with ethyl acetate, obtains clear crystal, yield 41%.Reaction equation
It is as follows：
(3) synthesis of N isopropyl 2,3,3- trimethyl -3H indoline
0.061molN isopropyl [2,3,3- trimethyl -3H- indoles] iodide are taken to be dissolved in 50mL dehydrated alcohol, to this
5mL triethylamine is added dropwise in solution, and is reacted 30 minutes at 90 DEG C of oil bath, solution is peony.Reaction equation is as follows：
(4) synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine
It takes and is dissolved in addition 10g active carbon in 100mL ethyl alcohol under 0.02mol1- nitroso-beta naphthal heating, boil 10 points
Clock filters while hot, obtains the 1-Nitroso-2-naphthol solution of transparent salmon, by 2,3,3- front three of step 3 product N isopropyl
Base -3H indoline is added in this reaction, is continued back flow reaction 3-4 hours.Cooling after reaction, dry, it is solid to obtain brown for recrystallization
Body product, yield 45%.Reaction equation is as follows：
Obtained brown solid product volume ratio is 1:The mixed solution dissolution of 1 ethyl alcohol and acetone, it is solid to obtain brown
Body, drying recrystallize repeatedly, obtain dark brown crystal.This product makees the test in later period.
Product carries out infrared spectrum characterization, and infrared spectroscopy is as shown in Figure 1, characterize data is as shown in table 1.
Table 1
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of isopropyl alkyl spirooxazine photochromic compound, it is characterised in that：Its chemical name is N isopropyl [2,3,3-
Trimethyl -3H- indoles] spirooxazine, structural formula is：
2. a kind of synthetic method of isopropyl alkyl spirooxazine photochromic compound, it is characterised in that：Include the following steps：
Step 1, the synthesis of 2,3,3- trimethyl -3H- indoles：It is anti-through flowing back using methyl isopropyl ketone and phenylhydrazine as reactant
Crude hydrazone should be obtained, by resulting hydrazone and strong sulfuric acid response, obtains 2,3,3- trimethyl -3H- indoles；Reaction equation is as follows:
Step 2, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] iodide：To take Iso-Propyl iodide and step 1 to obtain
2 arrived, 3,3- trimethyl -3H- indoles obtain N isopropyl [2,3,3- trimethyl -3H- indoles] through back flow reaction for reactant
Iodide；Reaction equation is as follows：
Step 3, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] indoline：Step 2 is obtained N isopropyl [2,
3,3- trimethyl -3H- indoles] iodide are dissolved in dehydrated alcohol, and triethylamine is added dropwise, and oil bath reacts to obtain N isopropyl -2,3,
3- trimethyl -3H indoline；Reaction equation is as follows：
Step 4, the synthesis of N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine：1-Nitroso-2-naphthol is heated down
It is dissolved in dehydrated alcohol, the orange-red solution of 1-Nitroso-2-naphthol is obtained by filtration, above-mentioned orange-red solution is obtained with step 3
Product obtain dark brown solid product through back flow reaction；Reaction equation is as follows：
3. the synthetic method of isopropyl alkyl spirooxazine photochromic compound according to claim 2, it is characterised in that：Institute
Stating step 1 is specially：
To be added in the phenylhydrazine being newly evaporated under reduced pressure by air-distillation methyl isopropyl ketone, this mixed liquor under stiring in
100 DEG C of back flow reactions, obtain crude hydrazone；Obtained hydrazone is reacted in oil bath with the concentrated sulfuric acid, by vacuum distillation, reaction
It finishes and is neutralized to alkalinity with NaOH, solution generates lamination；Water phase is separated with separatory funnel again and organic phase, organic phase are frequent
Pressure distillation removes solvent, then is evaporated under reduced pressure, and collects 126 DEG C, the fraction of 2000Pa, products therefrom is pale yellow oily liquid.
4. the synthetic method of isopropyl alkyl spirooxazine photochromic compound according to claim 2, it is characterised in that：Institute
Stating step 2 is specially：
It takes Iso-Propyl iodide and is mixed with 2,3, the 3- trimethyl -3H- indoles newly distilled, back flow reaction 3 is small in 110 DEG C of oil bath
When, it is filtered under diminished pressure after cooling and collects solid crude product；It grinds after drying, is repeatedly washed with ethyl alcohol；After drying again with ethyl acetate
Secondary washing, obtains clear crystal.
5. the synthetic method of isopropyl alkyl spirooxazine photochromic compound according to claim 2, it is characterised in that：Institute
Stating step 3 is specially：
It takes N isopropyl [2,3,3- trimethyl -3H- indoles] iodide to be dissolved in dehydrated alcohol, triethylamine is added dropwise into this solution,
And reacted 30 minutes at 90 DEG C of oil bath, obtain dark red solution.
6. the synthetic method of isopropyl alkyl spirooxazine photochromic compound according to claim 5, it is characterised in that：Institute
Stating step 4 is specially：
1-Nitroso-2-naphthol is heated down and is dissolved in dehydrated alcohol, and active carbon is added, boils 10 minutes, is obtained after filtering
The transparent salmon solution of 1-Nitroso-2-naphthol, the N isopropyl for then obtaining step 3 [2,3,3- trimethyl -3H- Yin
Diindyl] iodide are added in this reaction, continue back flow reaction 3-4 hour, and cooling after reaction, dry, recrystallization obtains dark brown and consolidates
Body product N isopropyl [2,3,3- trimethyl -3H- indoles] spirooxazine.
7. the synthetic method of isopropyl alkyl spirooxazine photochromic compound, feature according to claim 2 or 6 exist
In：In the step 4, the mixed solution of obtained brown solid product ethyl alcohol and acetone dissolves, then obtains after recrystallizing black
Brown solid.
8. the synthetic method of isopropyl alkyl spirooxazine photochromic compound according to claim 7, it is characterised in that：Institute
In the mixed solution for stating ethyl alcohol and acetone, the volume ratio of ethyl alcohol and acetone is 1：1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440193A (en) * | 2020-05-20 | 2020-07-24 | 南开大学 | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6363779A (en) * | 1986-09-05 | 1988-03-22 | Nissan Motor Co Ltd | Photochromic material |
-
2018
- 2018-05-22 CN CN201810494506.0A patent/CN108822129A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6363779A (en) * | 1986-09-05 | 1988-03-22 | Nissan Motor Co Ltd | Photochromic material |
Non-Patent Citations (4)
| Title |
|---|
| POTTIER, E. ET AL.: "Synthesis of some photochromic spiro[indoline-naphthoxazines] and spiro[indoline-pyridobenzoxazines]. Application of the experimental design methodology", 《BULLETIN DES SOCIETES CHIMIQUES BELGES》 * |
| 孙宾宾 等: "5-取代吲哚啉螺萘并噁嗪染料的合成与表征", 《印染助剂》 * |
| 安晶 等: "N-丙烯基螺恶嗪的合成与研究", 《工程塑料应用》 * |
| 安晶 等: "烯丙基螺恶嗪的合成", 《盐城工学院学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440193A (en) * | 2020-05-20 | 2020-07-24 | 南开大学 | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof |
| CN111440193B (en) * | 2020-05-20 | 2023-01-24 | 南开大学 | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof |
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