CN117865837A - Synthesis process of N, N', N"-tripentyl-1, 3, 5-triaminobenzaldehyde - Google Patents
Synthesis process of N, N', N"-tripentyl-1, 3, 5-triaminobenzaldehyde Download PDFInfo
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- CN117865837A CN117865837A CN202311864751.3A CN202311864751A CN117865837A CN 117865837 A CN117865837 A CN 117865837A CN 202311864751 A CN202311864751 A CN 202311864751A CN 117865837 A CN117865837 A CN 117865837A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- -1 N, N', N"-tripentyl-1, 3, 5-triaminobenzaldehyde Chemical compound 0.000 title claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims abstract description 8
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 5
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- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 12
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 229940032296 ferric chloride Drugs 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- 239000013384 organic framework Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis process of N, N', N"-trite acylation-1, 3, 5-triaminobenzaldehyde, N, N', N"-trite acylated-1, 3, 5-triaminobenzaldehyde is obtained by oxidizing a benzyl carbon hydrogen bond of N, N', N"-trite acylated-1, 3, 5-triaminobenzaldehyde to form an aldehyde group; the synthesis process comprises the following steps: N, N', N"-tripentylating-1, 3, 5-triaminoboluenes with FeCl 3 . 6H 2 O is added into a proper amount of dimethyl sulfoxide (DMSO) solvent to form a reaction system; transferring the reaction system to an environment of 20-25 ℃ for blue light irradiation, and continuously stirring to enable the reaction to be carried out for 18-24 hours; after the reaction is finished, separating N, N', N"-tripentyl-1, 3, 5-triaminobenzaldehyde from the reaction system. The synthesis process of the N, N', N"-tripentyl-1, 3, 5-triaminobenzaldehyde provided by the invention has mild synthesis conditions, and the synthesis process does not involve toxic reagents and transition metalsBelongs to the advantages of simple use and synthesis operation, high target selectivity, easy amplification of the synthesis process and the like, and is a sustainable strategy for synthesizing the aromatic aldehyde by benzyl oxidation.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a synthesis process of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde.
Background
Aromatic aldehyde is an important organic framework structure and plays an irreplaceable role in the production of fine chemicals such as pesticides, fragrances, medicines and the like. It differs from aliphatic aldehydes in that two single bonds on the carbonyl group, one attached to the aryl group and one attached to the hydrogen, form an aromatic aldehyde. The aromatic aldehyde is interposed between the alcohol and the acid, and can be further oxidized to synthesize benzoic acid or reduced to synthesize benzyl alcohol. Due to its structural versatility, aromatic aldehydes are often used as synthesis modules for important molecules, such as vesicle 2, 6-bis (7-benzamidoquinoline) pyridine derivatives.
From the current research results of aromatic aldehyde synthesis, most methods for synthesizing aromatic aldehyde by using a transition metal such as Co, au, ru, cr, ir, cu, V or Mn as a catalyst require an additional additive or severe conditions, particularly high temperature and high pressure, so that the sustainability and selectivity of the methods are limited. In addition, alkyl aromatic oxidation processes developed with permanganate, persulfate and t-butyl hydroperoxide as oxidants have lacked atomic economy.
Therefore, there is growing interest in developing green, efficient, low cost aromatic aldehyde synthesis methods.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis process of N, N '-trite-1, 3, 5-triaminobenzaldehyde, which is used for realizing green, efficient and low-cost synthesis of N, N' -trite-1, 3, 5-triaminobenzaldehyde.
The specific invention comprises the following steps:
the invention provides a synthesis process of N, N '-trite acylation-1, 3, 5-triaminobenzaldehyde, wherein the N, N', N '-trite acylated-1, 3, 5-triaminobenzaldehyde is obtained by oxidizing a benzyl carbon hydrogen bond of N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde to form an aldehyde group;
the synthesis process comprises the following steps:
n, N' -tripentylating-1, 3, 5-triaminoboluenes with FeCl 3 . 6H 2 O is added into a proper amount of dimethyl sulfoxide solvent to form a system to be reacted;
transferring the system to be reacted to an environment of 20-25 ℃ for blue light irradiation, and continuously stirring to enable the reaction to be carried out for 18-24 hours;
after the reaction is finished, separating N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde from a reaction system;
wherein the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene in the system to be reacted is 50mM-0.2M, and the FeCl 3 . 6H 2 The concentration of O is 5% -10% of the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene.
Alternatively, the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene is 0.1M, the FeCl 3 . 6H 2 The concentration of O is 5% of the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene.
Optionally, the blue light is provided by an LED lamp.
Optionally, the power of the LED lamp is 45W, and the wavelength of the blue light is 390-465nm.
Alternatively, the reaction temperature is 25 ℃ and the reaction time is 24 hours.
Optionally, the separating process includes: extracting the reaction system with saturated saline solution and dichloromethane, subjecting the organic layer to chromatography, extracting the reaction system, subjecting the organic layer to chromatography, or
And directly carrying out recrystallization treatment on the reaction system to obtain the N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde.
Optionally, the chromatographic treatment adopts a 200-300-mesh silica gel column for wet column purification; the recrystallization treatment is to drip the reaction system into water to be separated out and filtered.
Optionally, the reaction process employs TLC for monitoring of N, N', N "-trite acylated-1, 3, 5-triaminobenzaldehyde formation and confirmation of the reaction endpoint.
Optionally, the yield of the N, N', N "-trite acylated-1, 3, 5-triaminobenzaldehyde is greater than 50%.
Compared with the prior art, the invention has the following advantages:
the invention provides a synthesis process of N, N '-trite acylation-1, 3, 5-triaminobenzaldehyde, N, N', N '-trite acylated-1, 3, 5-triaminobenzaldehyde is obtained by oxidizing a benzyl carbon hydrogen bond of N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde to form an aldehyde group; the synthesis process comprises the following steps: n, N' -tripentylating-1, 3, 5-triaminoboluenes with FeCl 3 . 6H 2 O is added into a proper amount of dimethyl sulfoxide (DMSO) solvent to form a reaction system; transferring the reaction system to an environment of 20-25 ℃ for blue light irradiation, and continuously stirring to enable the reaction to be carried out for 18-24 hours; after the reaction is finished, separating N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde from the reaction system. N, N ', N "-tripentyl-1, 3, 5-triaminobenzaldehyde was synthesized as N, N-tripentyl-1, 3, 5-triaminobenzaldehyde (trade name: XT-386), in contrast to the conventional N, N ' -tripentylates-1, 3, 5-triaminobenzaldehyde preparation route, the present invention provides N, N ' -tripentylates-1, 3, 5-triaminobenzaldehydesThe synthesis process of the benzaldehyde has the advantages of extremely simple preparation route, mild synthesis conditions, no toxic reagent and transition metal in the synthesis process, simple synthesis operation, high target selectivity, high yield, easy amplification of the synthesis process and the like, and is a sustainable benzyl oxidation synthesis aromatic aldehyde strategy.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a process flow diagram of the synthesis of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde provided by the embodiment of the invention;
FIG. 2 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminoboluene provided by the embodiment of the invention 1 H NMR(DMSO,400MHz))；
FIG. 3 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminoboluene provided by the embodiment of the invention 13 C NMR(DMSO,101MHz))；
FIG. 4 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde according to an embodiment of the present invention 1 H NMR(DMSO,400MHz))；
FIG. 5 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde according to an embodiment of the present invention 13 C NMR(DMSO,101MHz))。
FIG. 6 shows an infrared spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. Any product that is the same as or similar to the present invention, which anyone in the light of the present invention or combines the present invention with other prior art features, falls within the scope of the present invention based on the embodiments of the present invention. And all other embodiments that may be made by those of ordinary skill in the art without undue burden and without departing from the scope of the invention.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge. Furthermore, the drawings are merely schematic illustrations of embodiments of the invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.
Techniques, methods and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the present description where appropriate.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for defining the components, and are merely for convenience in distinguishing the corresponding components, and the terms are not meant to have any special meaning unless otherwise indicated, so that the scope of the present invention is not to be construed as being limited.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Aromatic aldehydes not only play an important role in the derivatization of natural product molecules, but also play a pivotal role in the later modification of biologically active molecules. However, the existing method for preparing aromatic aldehyde by oxidizing alkyl aromatic hydrocarbon often requires the use of an external oxidant or a toxic reagent. These can oxidize alkyl aromatic hydrocarbon, but have a great environmental pollution. In addition, since the target aromatic aldehyde has a significantly higher oxidability than the alkyl aromatic hydrocarbon, inhibitors are required in the reaction process to prevent the generated target from being further oxidized to be lost.
Therefore, the existing methods for preparing aromatic aldehydes by oxidizing alkyl aromatic hydrocarbons are not economically ideal and require further improvement. The invention provides a process for synthesizing N, N '-trite-acylated-1, 3, 5-triaminobenzaldehyde from N, N' -trite-acylated-1, 3, 5-triaminobenzaldehyde by researching a benzyl hydrocarbon bond oxidation method, and has the advantages of mild synthesis conditions, no involvement of toxic reagents and transition metals in the synthesis process, simple synthesis operation, high target selectivity, easy amplification of the synthesis process and the like. The specific implementation content is as follows:
the invention provides a synthesis process of N, N '-tripentyl-1, 3, 5-triaminobenzaldehyde, N, N', N '-trite acylated-1, 3, 5-triaminobenzaldehyde is obtained by oxidizing a benzyl carbon hydrogen bond of N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde to form an aldehyde group; fig. 1 shows a process flow chart of the synthesis process of the N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde provided by the embodiment of the invention, and as shown in fig. 1, the synthesis process comprises the following steps:
step 1, N' -tripentylating-1, 3, 5-triaminoboluene and FeCl 3 . 6H 2 O is added into a proper amount of dimethyl sulfoxide (DMSO) solvent to form a system to be reacted;
step 2, transferring the system to be reacted to an environment of 20-25 ℃ for blue light irradiation, and continuously stirring to enable the reaction to be carried out for 18-24 hours;
and step 3, after the reaction is finished, separating N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde from the reaction system.
In specific implementation, the embodiment of the invention adopts N, N '-tripentyl-1, 3, 5-triaminoboluene (0.1M, 1 equiv) as a substrate to synthesize N, N' under the set primary reaction conditions "Optimization of the conditions for the trite acylation of 1,3, 5-triaminobenzaldehyde. The following optimization procedure was carried out with respect to the concentration of N, N' -tripentylated-1, 3, 5-triaminoboluene of 1 equivalent (equiv), to explain the relation of the amounts of the other reagents. The primary reaction conditions set include: feCl 3 As photosensitizer (0.1 equiv), TBACl as catalyst (0.1 equiv), cl 3 CCH 3 OH as additive (0.2 equiv), the solvent (0.1M) provided in Table 1 was selected to provide an oxygen atmosphere and irradiated with blue LEDs at 25℃for 24 hours. The reaction conditions and equations are shown in formula I:
TABLE 1 yields of target products in different solvents
As shown in Table 1, the present invention performs the reaction shown in equation I (see, in particular, SEQ ID NO: 1) under the reaction conditions shown in equation I, and the product is subjected to nuclear magnetism 1 H NMR identified that the system contained 3% yield of the target product. Further, after the solvent was changed, most of the solvents shown in table 1 did not allow the reaction to proceed, or only a trace amount of the product was produced. However, when the solvent was changed to DMSO, we detected 63% of the target product. Therefore, DMSO is selected as a solvent for further screening in the subsequent process, and the reaction conditions and equations are shown as formula II;
further, in order to verify the effect of trichloroethanol and tetrabutylammonium chloride on the reaction in the reaction conditions given by the formula II, the invention confirms the necessary conditions of the reaction. The results are shown in Table 2.
TABLE 2 essential condition control experiment
As is clear from Table 2, neither trichloroethanol nor tetrabutylammonium chloride has a promoting effect on the reaction. In addition, the reaction effect was better when neither was added, and the yield reached 89% (shown in sequence number 4). When air is substituted for oxygen, there is also a good result, and the yield is not greatly different from the case of using oxygen as the oxidizing agent. Because air is more convenient and safer than oxygen, in the following experiments, the invention uses air as an oxygen source for exploration, and the reaction conditions and equations are shown in the formula III:
next, the present invention verifies the catalytic effect of different iron salts on the reaction of formula iii, and the reaction of formula iii is performed by selecting different iron salt catalysts shown in table 3, and the results are shown in table 3.
TABLE 3 catalyst screening
As can be seen from table 3, the catalytic effect of other iron salts, except for ferric chloride, is poor, but it is interesting that ferric chloride with water of crystallization catalyzes the reaction with a slight increase in yield, presumably the presence of water prevents excessive oxidation of the reaction, so that the aldehyde content after the reaction is slightly higher than that of iron without water of crystallization (see shown in serial numbers 1, 2). The present invention further optimizes the catalyst to ferric chloride hexahydrate, considering that ferric chloride is easily absorbed in water and ferric chloride containing crystal water is easier to handle (ferric chloride is easily absorbed in water and thus difficult to weigh).
After the type of the catalyst is determined, the invention further confirms whether the content of the catalyst can be reduced, so that the reaction is more green and efficient. Thus, the catalyst loading was screened and the result was thatAs shown in table 4. FeCl expressed as n mol% 3 .6H 2 The O content is N% of the concentration of N, N' -tripentyl-1, 3, 5-triaminoboluene substrate.
TABLE 4 screening of catalyst amounts
It was found that the reaction yield was only slightly reduced when the catalyst loading was 5mol% (shown in SEQ ID NO: 5). Thus, the subsequent use of 5mol% catalyst was further optimized and the reaction conditions and equations are shown in formula V:
the solvent, catalyst, and catalyst loading of the reaction were determined and the present invention continued to explore whether there was room for improvement in the concentration of the reaction substrate. As a result, as shown in Table 5, the yield gradually decreased with increasing substrate concentration, and the yield was not significantly changed with a thinner concentration.
TABLE 5 screening of substrate concentrations
After experimental screening of various reaction conditions, the reaction conditions determined by the invention are as follows: n, N' -tripentylating-1, 3, 5-triaminoboluenes (50 mM-0.2M,1 equiv), feCl 3 . 6H 2 O (0.05-0.10 equiv). Namely, N, N' -tripentylating-1, 3, 5-triaminoboluenes with FeCl 3 . 6H 2 The molar ratio of O is 20:1-2. Preferred conditions are N, N', N "-tripentylates-1, 3, 5-triaminoboluenes (0.1M,1equiv)、FeCl 3 . 6H 2 o (0.05 equiv). Blue light may be provided by an LED lamp. The wavelength of blue light is 390-465nm.
In order to make the present invention more clearly understood by those skilled in the art, a process for synthesizing N, N' -tripentylase-1, 3, 5-triaminobenzaldehyde according to the present invention will be described in detail by the following examples.
The reagents used in the examples below were all of the reagent grade and purchased from Sigma Aldrich, alfa-Aesar, an Naiji, pide, leyan, and other reagent companies, and were used without further purification unless otherwise specified. The nitrogen, argon and oxygen used in the experiment were supplied by Nanchang Hongwei gas company. TLC analysis was performed using a 0.20mm thick GF254 silica gel plate (nictita, bevanda silica gel ltd) with 254nm fluorescent indicator. TLC plates were prepared by UV lamp or with alkaline potassium permanganate reagent (KMnO 4 、K 2 CO 3 、NaOH、H 2 O) color development. The purification of the general products is carried out by silica gel (200-300 meshes) fast column chromatography, and for the crude product system which is large in quantity and not easy to separate, the silica gel powder (300-400 meshes) can be used as column chromatography stationary phase, and the crude product system which is small in quantity and not easy to separate can be used<50 mg) can be isolated and purified using PTLC. The mobile phase solvent of column chromatography is n-hexane, ethyl acetate, dichloromethane, methanol, etc., and is subjected to low temperature re-evaporation before use. The solvent used for nuclear magnetic resonance measurement is CDCl provided by Beijing Inock reagent company 3 (TMS, 1 Hδ＝0；CDCl 3 , 1 Hδ＝7.26, 13 Cδ=7.16) or DMSO-d6 (TMS, 1 Hδ＝0；DMSO-d6, 1 Hδ＝2.50, 13 cδ=39.2). Chemical shifts (δ) of the spectral data are reported in ppm, coupling constants (J) in Hz, and the following abbreviations are used to represent peak multiplicity: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet.
Example 1
To a dried 10mL schlenk tube with a magneton, trite (0.2 mmol,1.0 equiv) was added sequentially FeCl 3 . 6H 2 O (2.7 mg,5 mol%) and DMSO (2 mL) were added. At the position ofStirring at normal temperature for 24h under the irradiation of a blue LED lamp (45W, 390 nm) at 25 ℃, extracting with dichloromethane and saturated saline after the reaction is completed, concentrating an organic layer under reduced pressure, and purifying a crude product by a silica gel column chromatography (200-300 meshes) wet method through a column to obtain N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde with the yield of 84%.
Example 2
To a dried 10ml schlenk tube with a magneton was added sequentially trite (0.2 mol,1.0 equiv) FeCl 3 . 6H 2 O (5.4 mg,10 mol) was added to DMSO (2 mL). Stirring at normal temperature for 24h under the irradiation of a blue LED lamp (45W, 390 nm) at 25 ℃, extracting with dichloromethane and saturated saline after the reaction is completed, concentrating the organic layer under reduced pressure, and purifying the crude product by a silica gel column chromatography (200-300 meshes) wet method through a column to obtain N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde with the yield of 89%.
Example 3
To a dried 10ml schlenk tube with a magneton was added sequentially trite (0.2 mol,1.0 equiv) FeCl 3 . 6H 2 O (4.1 mg,7.5 mol%) and DMSO (2 mL) were added. Stirring at normal temperature for 24h under the irradiation of a blue LED lamp (45W, 390 nm) at 25 ℃, extracting with dichloromethane and saturated saline after the reaction is completed, concentrating the organic layer under reduced pressure, and purifying the crude product by a silica gel column chromatography (200-300 meshes) wet method through a column to obtain N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde with the yield of 86%.
Example 4
To a dried 250mL round bottom flask with a magnet was added N, N', N "-tripentyl-1, 3, 5-triaminoboluene (5.0 g,12.84 mmol), feCl in sequence 3 . 6H 2 O (173.53 mg,5 mol%) and DMSO (128.4 mL) were added. Stirring at 25deg.C under irradiation of blue LED lamp (45W, 460 nm) at normal temperature for 24 hr, monitoring reaction progress by TLC, adding 600mL H after reaction is complete 2 O is crystallized to separate out white solid, and then 4.61g of target product is obtained by suction filtration, and the yield is 89%.
FIG. 2 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminoboluene provided by the embodiment of the invention 1 H NMR(DMSO,400 MHz)); FIG. 3 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminoboluene provided by the embodiment of the invention 13 C NMR (DMSO, 101 MHz)); FIG. 4 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde according to an embodiment of the present invention 1 H NMR (DMSO, 400 MHz)); FIG. 5 shows a nuclear magnetic resonance hydrogen spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde according to an embodiment of the present invention 13 C NMR (DMSO, 101 MHz)); FIG. 6 shows an infrared spectrum of N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde provided by an embodiment of the invention. All of the above examples 1-3 use air as the oxygen source, and do not require high temperature and high pressure, and use inexpensive and readily available FeCl 3 . 6H 2 O is used as a photosensitizer, dimethyl sulfoxide is used as a solvent, so that the reaction process is well stopped at an aldehyde stage and cannot be excessively oxidized to benzoic acid, and the preparation of N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde is realized in a high (more than 80%) yield.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, one skilled in the art can combine and combine the different embodiments or examples described in this specification.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The above description is made in detail of a synthesis process of N, N-trite-1, 3, 5-triaminobenzaldehyde provided by the present invention, and specific examples are applied herein to illustrate the principles and embodiments of the present invention, the above examples are only for helping to understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. A process for synthesizing N, N '-tripentyl-1, 3, 5-triaminobenzaldehyde, which is characterized in that the N, N', N '-trite acylated-1, 3, 5-triaminobenzaldehyde is obtained by oxidizing a benzyl carbon hydrogen bond of N, N' -trite acylated-1, 3, 5-triaminobenzaldehyde to form an aldehyde group;
the synthesis process comprises the following steps:
n, N' -tripentylating-1, 3, 5-triaminoboluenes with FeCl 3 . 6H 2 O is added into a proper amount of dimethyl sulfoxide solvent to form a system to be reacted;
transferring the system to be reacted to an environment of 20-25 ℃ for blue light irradiation, and continuously stirring to enable the reaction to be carried out for 18-24 hours;
after the reaction is finished, separating N, N' -tripentyl-1, 3, 5-triaminobenzaldehyde from a reaction system;
wherein the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene in the system to be reacted is 50mM-0.2M, and the FeCl 3 . 6H 2 The concentration of O is 5% -10% of the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene.
2. The synthesis process according to claim 1, wherein the concentration of N, N' -tripentyl-1, 3, 5-triaminoboluene is 0.1M, the FeCl 3 . 6H 2 The concentration of O is 5% of the concentration of the N, N' -tripentyl-1, 3, 5-triaminoboluene.
3. The synthesis process according to claim 1, wherein the blue light is provided by an LED lamp.
4. A synthesis process according to claim 3, wherein the power of the LED lamp is 45W and the wavelength of the blue light is 390-465nm.
5. The synthetic process of claim 1 wherein the reaction temperature is 25 ℃ and the reaction time is 24 hours.
6. The synthetic process of claim 1 wherein the separation process comprises: extracting the reaction system with saturated saline solution and dichloromethane, collecting organic layer, performing chromatography, or
And directly carrying out recrystallization treatment on the reaction system to obtain the N, N, N-tripentyl-1, 3, 5-triaminobenzaldehyde.
7. The synthetic process of claim 6 wherein the chromatographic treatment is wet column purification using a 200-300 mesh silica gel column.
8. The synthesis process according to claim 6, wherein the recrystallization treatment is precipitation by dropping the reaction system into water and filtration.
9. The synthetic process according to claim 1, wherein the reaction process employs TLC for monitoring of N, N-trite acylated-1, 3, 5-tri-aminobenzaldehyde formation and confirmation of reaction endpoint.
10. The synthetic process of claim 1 wherein the yield of N, N-trite acylated-1, 3, 5-triaminobenzaldehyde is greater than 50%.
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