CN110003089B - 3-hydroxymethyl-9-substituted carbazole and preparation method thereof - Google Patents
3-hydroxymethyl-9-substituted carbazole and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of 3-hydroxymethyl-9-substituted carbazole. A mL of DMSO, B mol of paraformaldehyde, C mol of sodium ethoxide and D mL of absolute ethyl alcohol are sequentially added into a dry 100mL three-neck flask under the cooling of an ice salt bath, the mixture is stirred, after the solid is dissolved, an E mol of N-alkyl carbazole DMSO solution is quickly dropped, A: E = (100-300): 1, C: D =1:8, B: C: E =1:1.5:1, and the reaction is stopped by using a few drops of concentrated hydrochloric acid after 3min of reaction. Then adding distilled water, separating out solid, filtering, washing and drying to obtain the crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain the pure product of 3-hydroxymethyl-9-substituted carbazole. The method has the advantages of simple operation, short reaction time, high product purity, high yield, mild reaction conditions, safety and environmental protection, and has important significance for the synthesis and development of the compounds.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to 3-hydroxymethyl-9-substituted carbazole and a preparation method thereof.
Background
Carbazole is a nitrogen-containing aromatic heterocyclic compound with a rigid conjugated planar structure, and various functional groups are easily introduced into a molecular skeleton, so that carbazole can be used as an antibacterial agent, a fluorescent material and the like. Carbazole and its derivatives have been widely used in the fields of medicine, fuel, polymer materials, and the like.
The existing aldehyde-alcohol reduction method introduces hydroxymethyl, and has the disadvantages of rigorous experimental conditions, poor selectivity and high price. Therefore, the method for preparing the 3-hydroxymethyl-9-substituted carbazole, which has simple process, high yield and low cost, has certain significance.
Disclosure of Invention
The invention aims to provide a preparation method for preparing 3-hydroxymethyl-9-substituted carbazole, which has the advantages of simple and safe operation, high yield, mild reaction conditions and short reaction time.
In order to achieve the purpose, the invention adopts the technical scheme that:
the general structural formula of the 3-hydroxymethyl-9-substituted carbazole is as follows:
wherein R is CH3，C2H5，n-C3H7，n-C12H25，n-C14H29，n-C16H33.
The preparation method of the 3-hydroxymethyl-9-substituted carbazole comprises the following steps:
a mL of DMSO, B mol of paraformaldehyde, C mol of sodium ethoxide and D mL of absolute ethyl alcohol are sequentially added into a dry 100mL three-neck flask under the cooling of an ice salt bath, the mixture is stirred, after the solid is dissolved, an E mol of N-alkyl carbazole DMSO solution is quickly dropped, A: E = (100-300): 1, C: D =1:8, B: C: E =1:1.5:1, and the reaction is stopped by using a few drops of concentrated hydrochloric acid after 3min of reaction. Then adding distilled water, separating out solid, filtering, washing and drying to obtain the crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain the pure product of the 3-hydroxymethyl-9-substituted carbazole.
The structural general formula of the N-alkyl carbazole is as follows:
wherein R is CH3，C2H5，n-C3H7，n-C12H25，n-C14H29，n-C16H33.
Adding distilled water, wherein the dosage of DMSO is A mL, and the ratio of distilled water: DMSO =1.5:1.
The few drops of concentrated hydrochloric acid were 3 drops.
Compared with the prior art, the invention has the beneficial effects that:
the carbazole enhances the electron-rich property because of the existence of N at the 9-position, and the hydroxymethyl group is introduced at the 3-position, so that a high-activity intermediate is provided, other groups are continuously introduced, and the derivative with a larger pi-electron conjugated system can be obtained.
The preparation method of 3-hydroxymethyl-9-substituted carbazole provided by the invention takes N-alkyl carbazole and paraformaldehyde as raw materials, sodium ethoxide as a catalyst, and DMSO as a solvent, and 3-hydroxymethyl-9-substituted carbazole can be prepared in a short time. The method has the advantages of mild reaction conditions, short reaction time, high yield, simple post-treatment, high product purity and great application prospect.
Drawings
FIG. 1 is an IR spectrum of 3-hydroxymethyl-9-methylcarbazole prepared in example 1
FIG. 2 is an IR spectrum of 3-hydroxymethyl-9-ethylcarbazole prepared in example 2
FIG. 3 is an IR spectrum of 3-hydroxymethyl-9-propylcarbazole prepared in example 3
FIG. 4 is an IR spectrum of 3-hydroxymethyl-9-dodecylcarbazole prepared in example 4
FIG. 5 is an IR spectrum of 3-hydroxymethyl-9-tetradecylcarbazole prepared in example 5
FIG. 6 is an IR spectrum of 3-hydroxymethyl-9-hexadecylcarbazole prepared in example 6
FIG. 7 is a drawing of 3-hydroxymethyl-9-methylcarbazole prepared in example 11HNMR spectrogram
FIG. 8 is a drawing of 3-hydroxymethyl-9-ethylcarbazole prepared in example 21HNMR spectrogram
FIG. 9 is a drawing of 3-hydroxymethyl-9-propylcarbazole prepared in example 31HNMR spectrogram
FIG. 10 shows the preparation of 3-hydroxymethyl-9-dodecylcarbazole in example 41HNMR spectrogram
FIG. 11 is a drawing of 3-hydroxymethyl-9-tetradecylcarbazole prepared in example 51HNMR spectrogram
FIG. 12 is a drawing of 3-hydroxymethyl-9-hexadecylcarbazole prepared in example 61HNMR spectrogram.
Detailed Description
The following is a further detailed description of the invention with reference to examples:
the invention takes N-alkyl carbazole and paraformaldehyde as raw materials, DMSO as a solvent and sodium ethoxide as a catalyst to prepare a series of 3-hydroxymethyl-9-substituted carbazoles in a short time. The reaction equation is as follows:
wherein R is CH3，C2H5，n-C3H7，n-C12H25，n-C14H29，n-C16H33.
Example 13 preparation of hydroxymethyl-9-methylcarbazole:
in a dry 100mL three-neck flask, 20 mL DMSO, 84mg (2.8mmol) paraformaldehyde, 285.8mg (4.2mmol) sodium ethoxide and 2 mL absolute ethyl alcohol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (2.8mmol) N-methylcarbazole is dissolved in 5mL DMMSO, quickly dropped into a reaction system, and after 3min of reaction, 3 drops of concentrated hydrochloric acid are dropped to terminate the reaction. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain pure yellow solid 3-hydroxymethyl-9-methylcarbazole. The yield is 90.7%, and the melting point is 87.9-91.2 ℃.
IR (KBr) v 3400(-OH), 3047 (benzene ring C-H), 2931, 2881 (saturated C-H), 1600, 1475 (benzene ring skeleton vibrating), 1411 (-CH)3Bending vibration), 1325(C-N).
1H NMR (400MHz, DMSO): δ 8.08(t,2H),7.52(t,2H),7.45(t,2H), 7.19(t, 1H), 5.16(t, 1H), 4.67(d, 2H), 3.86(s, 3H).
EXAMPLE 23 preparation of hydroxymethyl-9-ethylcarbazole
In a dry 100mL three-neck flask, 20 mL DMSO, 78mg (2.6mmol) paraformaldehyde, 265mg (3.9mmol) sodium ethoxide and 2 mL absolute ethyl alcohol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (2.6mmol) N-ethylcarbazole is dissolved in 5mL DMMSO, the mixture is quickly dripped into a reaction system, and after 3min of reaction, 3 drops of concentrated hydrochloric acid are dripped to terminate the reaction. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain pure yellow solid 3-hydroxymethyl-9-ethyl carbazole. The yield is 81.4%, and the melting point is 70.5-75.1 ℃.
IR (KBr) v 3402(-OH), 3047 (benzene ring C-H), 2976, 2866 (saturated C-H), 1600, 1465 (benzene ring skeleton vibration), 1377 (-CH)3Bending vibration), 1328(C-N).
1H NMR (400MHz, DMSO): δ 8.11(t,2H),7.53(t,2H),7.43(t,2H), 7.18(t, 1H), 5.19(t, 1H), 4.69(d, 2H), 4.40(d,2H),1.28(s, 3H).
EXAMPLE 33 preparation of hydroxymethyl-9-propylcarbazole
In a dry 100mL three-neck flask, 20 mL DMSO, 72mg (2.4mmol) paraformaldehyde, 245mg (3.6mmol) sodium ethoxide and 2 mL absolute ethyl alcohol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (2.4mmol) N-propyl carbazole is dissolved in 5mL DMMSO, the mixture is quickly dripped into a reaction system, and after 3min of reaction, 3 drops of concentrated hydrochloric acid are dripped to terminate the reaction. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain pure yellow solid 3-hydroxymethyl-9-propylcarbazole. The yield is 77.5%, and the m.p. is 94.3-95.0 ℃.
IR (KBr) v 3386(-OH), 3039 (benzene ring skeleton vibration), 2923, 2877 (saturated C-H), 1602, 1465 (benzene ring skeleton vibration), 1377 (-CH)3Flexural vibration), 1328(C-N).
1H NMR(400MHz,DMSO):δ8.08-8.12(t,1H),7.54(q,2H),7.42(t,2H), 7.17(t, 1H), 5.14(s, 1H), 4.65(s, 2H), 4.34(t,2H),1.78(t,2H),0.85(s, 3H)。
EXAMPLE 43 preparation of hydroxymethyl-dodecylcarbazole
In a dry 100mL three-neck flask, 20 mL of DMSO, 45mg (1.5mmol) of paraformaldehyde, 153mg (2.25mmol) of sodium ethoxide and 1 mL of absolute ethanol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (1.5mmol) of N-dodecyl carbazole is dissolved in 5mL of DMMSO, the mixture is quickly dripped into a reaction system, and after 3min of reaction, 3 drops of concentrated hydrochloric acid are dripped to terminate the reaction. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain a pure white solid 3-hydroxymethyl-9-dodecyl carbazole. Yield 84.3%, m.p. 65-66 ℃.
IR (KBr) v 3269(-OH), 3055 (benzene ring C-H), 2920, 2850 (saturated C-H), 1602, 1469 (benzene ring skeleton vibration), 1336(-CH3 bending vibration), 1001 (primary alcohol C-O).
1H NMR (400 MHz, DMSO) δ 8.21-8.01 (m, 2H), 7.66 -7.49 (m, 2H), 7.43 (t, 2H), 7.17 (t, 1H), 5.17 (t, 1H), 4.65 (d, 2H), 4.37 (t, 2H), 1.75 (s, 2H), 1.34 -1.07 (m, 18H), 0.85 (t, 3H).
EXAMPLE 53 preparation of hydroxymethyl-9-tetradecylcarbazole
In a dry 100mL three-neck flask, 20 mL DMSO, 42mg (1.4mmol) paraformaldehyde, 143mg (2.1mmol) sodium ethoxide and 1 mL absolute ethyl alcohol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (1.4mmol) N-tetradecylcarbazole is dissolved in 5mL DMMSO, quickly dropped into a reaction system, and 3 drops of concentrated hydrochloric acid are dropped to terminate the reaction after 3min of reaction. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain a pure white solid 3-hydroxymethyl-9-tetradecylcarbazole. The yield was 79.2%, m.p. 62-62 ℃.
IR (KBr) v 3267(-OH), 3049 (benzene ring C-H), 2920, 2854 (saturated C-H), 1608, 1471 (benzene ring skeleton vibration), 1348(-CH3 bending vibration), 1070 (primary alcohol C-O).
1H NMR (400 MHz, DMSO) δ 8.09 (m, 2H), 7.55 (dd, 2H), 7.43 (dd, 2H), 7.17 (t, 1H), 5.15 (t, 1H), 4.64 (t, 2H), 4.37 (t, 2H), 1.75 (m, 2H), 1.22(dd, 22H), 0.85 (t, 3H).
EXAMPLE 63 preparation of hydroxymethyl-9-hexadecylcarbazole
In a dry 100mL three-neck flask, 20 mL DMSO, 39mg (1.3mmol) paraformaldehyde, 133mg (1.95mmol) sodium ethoxide and 1 mL absolute ethyl alcohol are sequentially added under the cooling of an ice salt bath, stirred and dissolved, 500mg (1.3mmol) N-hexadecyl carbazole is dissolved in 5mL DMMSO, the N-hexadecyl carbazole is quickly dropped into a reaction system, and 3 drops of concentrated hydrochloric acid are dropped to terminate the reaction after the reaction is carried out for 3 min. Then adding 30mL of distilled water, separating out solids, carrying out suction filtration, washing with water, and drying to obtain a crude product. Recrystallizing the crude product with absolute ethyl alcohol to obtain a pure white solid 3-hydroxymethyl-9-hexadecyl carbazole. The yield was 88.5%, m.p. 59-60 ℃.
IR (KBr) v 3325(-OH), 3051 (benzene ring C-H), 2918, 2850 (saturated C-H), 1602, 1471 (benzene ring skeleton vibration), 1336 (-CH)3Flexural vibrations), 1006 (primary alcohols C-O).
1H NMR (400 MHz, DMSO) δ 8.14 (m, 2H), 7.58 (dd, 2H), 7.45 (t, 2H), 7.20 (t, 1H), 5.18 (t, 1H), 4.68 (d, 2H), 4.40 (t, 2H), 1.78 (s, 2H), 1.23(d, 26H), 0.88 (t, 3H)。
Claims (7)
1. A preparation method of 3-hydroxymethyl-9-substituted carbazole is characterized by comprising the following steps:
under the ice bath condition, dissolving sodium ethoxide and paraformaldehyde in ethanol, adding a DMSO solution of N-alkyl carbazole, and reacting the N-alkyl carbazole and the paraformaldehyde in the DMSO solution by taking the sodium ethoxide as a catalyst to obtain 3-hydroxymethyl-9-substituted carbazole;
the structural formula of the N-alkyl carbazole is as follows:
in the formula, R is CH3、C2H5、n-C3H7、n-C12H25、n-C14H29Or n-C16H33。
2. The method as claimed in claim 1, wherein after the N-alkyl carbazole is prepared into a DMSO solution of 0.1-0.2 g/mL, an ethanol solution in which paraformaldehyde and sodium ethoxide are dispersed is dropped into the DMSO solution of the N-alkyl carbazole to start the reaction.
3. The method according to claim 1, wherein the concentration of sodium ethoxide in ethanol is 0.15 g/mL.
4. The method according to claim 1, wherein the reaction is terminated by adding an appropriate amount of concentrated hydrochloric acid 3min after the reaction initiation time.
5. The method of claim 1, wherein after the reaction is finished, adding a proper amount of distilled water to separate out a product, performing suction filtration, washing with water, and drying to obtain a crude product; recrystallizing the crude product with anhydrous ethanol to obtain the pure product.
6. The method of claim 1, wherein the molar ratio of paraformaldehyde, sodium ethoxide, and N-alkyl carbazole is 1:1.5: 1.
7. The method according to claim 1, characterized in that the specific steps comprise:
adding DMSO A mL, paraformaldehyde B mol, sodium ethoxide C mol and absolute ethyl alcohol D mL into a dry three-neck flask with ice salt bath cooling in sequence, stirring, dissolving the solid, quickly dropping an N-alkyl carbazole E mol DMSO solution A: E = (100-300): 1, C: D =1:8, B: C: E =1:1.5:1, reacting for 3min, and terminating the reaction by using a few drops of concentrated hydrochloric acid; after the reaction is finished, adding a proper amount of distilled water to separate out a product, and performing suction filtration, water washing and drying to obtain a crude product; recrystallizing the crude product with anhydrous ethanol to obtain the pure product.
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