CN110256365A - The method that cyclopentadienyl titanium dichloride catalysis prepares Benzodiazepine derivative - Google Patents

The method that cyclopentadienyl titanium dichloride catalysis prepares Benzodiazepine derivative Download PDF

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CN110256365A
CN110256365A CN201910548655.5A CN201910548655A CN110256365A CN 110256365 A CN110256365 A CN 110256365A CN 201910548655 A CN201910548655 A CN 201910548655A CN 110256365 A CN110256365 A CN 110256365A
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titanium dichloride
benzodiazepine
cyclopentadienyl titanium
compound
prepares
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CN110256365B (en
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高子伟
杨明明
苏洁
庄梦媛
孙华明
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Shaanxi Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
    • C07D243/12—1,5-Benzodiazepines; Hydrogenated 1,5-benzodiazepines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses a kind of methods that cyclopentadienyl titanium dichloride catalysis prepares benzodiazepine compound, this method is using 3- crotonylene -one class compound and o-phenylenediamine class compound as raw material, using ethyl alcohol or methanol as solvent and promotor, using cyclopentadienyl titanium dichloride as catalyst, using M-phthalic acid, 2- hydroxy niacin or salicylic acid as ligand, efficiently high yield it can prepare 2,4- diphenyl -3-H-1,5- Benzodiazepine derivative.Used catalyst dosage of the present invention is few, it is cheap, nontoxic, to air-stable, reaction condition is mild, the time is short, it is easy to operate, only product need to be passed through simple column chromatography for separation after reaction, can be obtained 2,4- diphenyl -3-H-1,5- Benzodiazepine derivative is 2,4- diphenyl -3-H-1, the preparation of 5- Benzodiazepine derivative opens the approach of new low cost and green high-efficient, has broad application prospects.

Description

The method that cyclopentadienyl titanium dichloride catalysis prepares Benzodiazepine derivative
Technical field
The invention belongs to the synthesis technical fields of benzodiazepine compound, and in particular to a kind of M-phthalic acid, 2- hydroxyl Base niacin or salicylic acid are as ligand promotion cyclopentadienyl titanium dichloride catalysis 3- crotonylene -one class compound and o-phenylenediamine class compound Reaction, efficiently prepares the method for benzodiazepine compound.
Background technique
Benzodiazepine compound is a kind of alkaloid compound being widely present, the bioactivity having by it and height Pharmacological activity be used in multiple fields, including alcohol withdrawal symptom, insomnia, anxiety disorder, anti-inflammatory, anti-spasm, sedative and Analgesic, some of them can be used to treating cancer, cardiovascular disease and AIDS.
At present the synthetic method of benzodiazepine compound substantially there are three types of, be 1,3- cyclohexadione compounds and adjacent benzene respectively Diamine reactant, nitrile group or other unsaturated functional groups are reacted with o-phenylenediamine, ketenes or acetylene are reacted with o-phenylenediamine.It is existing These methods use harsher reaction condition such as strong acid, highly basic or microwave assisting method, the metallic catalyst used mostly Also in place of having the deficiencies of dosage is big, expensive, therefore, develop a kind of catalyst is cheap, dosage is few, it is environmentally friendly, stable, Efficiently, the catalysis process of mild condition is of great significance to the preparation of benzodiazepine compound.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome to lack existing for existing benzodiazepine compound preparation method Point, provide it is a kind of it is easy to operate, reaction condition is mild, substrate applicability is wide, the efficient Benzodiazepine for preparing spreads out the side of class compound Method.
Solving technical solution used by above-mentioned technical problem is: by the -one class compound of 3- crotonylene shown in Formulas I and Formula II Shown o-phenylenediamine class compound is added in organic solvent, and cyclopentadienyl titanium dichloride and ligand is added, and it is small to react 6~24 at room temperature When, product is isolated and purified, benzodiazepine compound shown in formula III is obtained；
R in formula1And R2Aryl or substituted aryl independent, specifically such as: table phenyl, C1~C4Alkyl-substituted phenyl, C1 ~C4Alkoxy substituted phenyl, halogenophenyl, trifluoromethyl substituted-phenyl, nitro substituted-phenyl etc.；R3、R4、R5、R6It is respectively independent Representative H, C1~C4Alkyl, C1~C4Any one in alkoxy, F, Cl, Br.
Above-mentioned organic solvent is ethyl alcohol, any one in methanol, preferred alcohol.
Above-mentioned ligand is M-phthalic acid, 2- hydroxy niacin, any one in salicylic acid, preferably M-phthalic acid.
In above-mentioned preparation method, preferably the molar ratio of 3- crotonylene -one class compound and o-phenylenediamine class compound is 1: 1.1~1.5.
In above-mentioned preparation method, the additional amount of preferably cyclopentadienyl titanium dichloride is the 1% of 3- crotonylene -one class compound mole ~3%.
In above-mentioned preparation method, the additional amount of preferably ligand is the 2%~6% of 3- crotonylene -one class compound mole.
The present invention is using ethyl alcohol or methanol as solvent, using cyclopentadienyl titanium dichloride as catalyst, with M-phthalic acid, 2- hydroxy niacin Or salicylic acid is ligand, can efficient catalytic 3- crotonylene -one class compound and o-phenylenediamine class compound directly react and obtain benzene Diazepine compound.Used catalyst dosage of the present invention is few, it is inexpensive, nontoxic, to air-stable, reaction condition is mild, the time Short, nontoxic solvent is easy to operate, and Atom economy is high, only product need to be passed through simple column chromatography for separation after reaction, i.e., The benzodiazepine compound with extensive bioactivity and medical value can be obtained, is the preparation of benzodiazepine compound The approach for opening new low cost and green high-efficient, has broad application prospects.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities Apply example.
Embodiment 1
The following 2,4- diphenyl -3-H-1,5- Benzodiazepine of preparation structure formula
0.0025g (0.01mmol) cyclopentadienyl titanium dichloride, 0.0033g (0.02mmol) isophthalic diformazan are added into reaction flask Acid, 0.065g (0.6mmol) o-phenylenediamine, 0.103g (0.5mmol) Isosorbide-5-Nitrae-diphenyl -3- crotonylene -one, 1mL ethyl alcohol, room temperature Under be stirred to react 5 hours, stop reaction, rotary evaporation remove ethyl alcohol, with silica gel post separation, (washing and dehydrating integrated machine is petroleum ether and acetic acid second Ester volume ratio is the mixed liquor of 10:1), obtain 2,4- diphenyl -3-H-1,5- Benzodiazepine, yield 96%, the wave of product Modal data are as follows:1H NMR(600MHz,CDCl3) δ 7.95-7.81 (m, 4H), 7.53 (dd, J=6.1,3.5Hz, 2H), 7.387.31 (m, 6H), 7.27 (dd, J=6.1,3.5Hz, 2H), 7.18 (s, 0H), 1.53 (s, 1H)；13C NMR(101MHz, CDCl3)δ154.26,140.83,137.34,130.69,128.83,128.77,128.22,125.54,35.01.
Comparative example 1
In embodiment 1, ethyl alcohol used is replaced with isometric toluene, and other steps are same as Example 1, can not obtain To 2,4- diphenyl -3-H-1,5- Benzodiazepine.
Comparative example 2
In embodiment 1, ethyl alcohol used is replaced with isometric DMF, and other steps are same as Example 1, obtain The yield of 2,4- diphenyl -3-H-1,5- Benzodiazepine is 28%.
Embodiment 2
The following 2- of preparation structure formula (4- fluorophenyl) -4- phenyl -3-H-1,5- Benzodiazepine
In the present embodiment, used in equimolar 1- (4- fluorophenyl) -4- phenyl -3- crotonylene -one alternative embodiment 1 Isosorbide-5-Nitrae-diphenyl -3- crotonylene -one, other steps are same as Example 1, obtain 2- (4- fluorophenyl) -4- phenyl -3-H-1, 5- Benzodiazepine, yield 98%, the spectral data of product are as follows:1H NMR(400MHz,CDCl3) δ 7.97 (ddd, J=7.7, 4.9,2.0Hz, 4H), 7.62 (dtd, J=7.5,3.5,1.8Hz, 2H), 7.43 (dd, J=5.2,2.0Hz, 3H), 7.35 (dd, J=6.2,3.5Hz, 2H), 7.09 (t, J=8.6Hz, 2H)；13C NMR(101MHz,CDCl3)δ165.55,163.05, 153.95,152.78,140.72,140.59,137.22,133.58,133.55,130.74,130.37,130.28,128.79, 128.72,128.18,128.14,125.56,115.87,115.66,34.94.
Embodiment 3
The following 2- of preparation structure formula (4- chlorphenyl) -4- phenyl -3-H-1,5- Benzodiazepine
In the present embodiment, used in equimolar 1- (4- chlorphenyl) -4- phenyl -3- crotonylene -one alternative embodiment 1 Isosorbide-5-Nitrae-diphenyl -3- crotonylene -one, other steps are same as Example 1, obtain 2- (4- chlorphenyl) -4- phenyl -3-H-1, 5- Benzodiazepine, yield 98%, the spectral data of product are as follows:1H NMR(400MHz,CDCl3) δ 7.96 (dd, J=7.5, 2.3Hz, 2H), 7.91 (d, J=8.6Hz, 2H), 7.65-7.57 (m, 2H), 7.46-7.41 (m, 3H), 7.39 (s, 1H), 7.38-7.32(m,3H)；13C NMR(101MHz,CDCl3)δ153.90,152.68,140.76,140.47,137.15, 136.91,135.70,130.78,129.45,128.95,128.80,128.73,128.16,125.69,125.58,34.82.
Embodiment 4
The following 2- of preparation structure formula (4- methoxyphenyl) -4- phenyl -3-H-1,5- Benzodiazepine
In the present embodiment, with equimolar 1- phenyl -4- (4- methoxybenzene phenyl) -3- crotonylene -one alternative embodiment 1 Used in Isosorbide-5-Nitrae-diphenyl -3- crotonylene -one, other steps are same as Example 1, obtain 2- (4- methoxyphenyl) -4- Phenyl -3-H-1,5- Benzodiazepine, yield 98%, the spectral data of product are as follows:1H NMR(400MHz,CDCl3)δ7.85 (dd, J=9.6,6.4Hz, 4H), 7.56-7.44 (m, 2H), 7.34-7.26 (m, 3H), 7.26-7.17 (m, 2H), 6.80 (d, J =8.7Hz, 2H), 3.70 (s, 3H)；13C NMR(101MHz,CDCl3)δ161.69,154.31,153.59,140.69, 137.44,130.58,130.00,129.94,128.79,128.72,128.14,125.46,125.12,114.07,55.40, 34.79.
Embodiment 5
The following 2- of preparation structure formula (4- aminomethyl phenyl) -4- phenyl -3-H-1,5- Benzodiazepine
In the present embodiment, with institute in equimolar 1- (4- aminomethyl phenyl) -4- phenyl -3- crotonylene -one alternative embodiment 1 Isosorbide-5-Nitrae-diphenyl -3- crotonylene -one, other steps are same as Example 1, obtain 2- (4- aminomethyl phenyl) -4- phenyl -3- H-1,5- Benzodiazepine, yield 99%, the spectral data of product are as follows:1H NMR(400MHz,CDCl3) δ 7.82 (dd, J= 6.7,3.0Hz, 2H), 7.72 (d, J=8.2Hz, 2H), 7.48 (dt, J=5.8,2.2Hz, 2H), 7.26-7.21 (m, 3H), 7.21-7.15 (m, 2H), 7.04 (d, J=8.0Hz, 2H), 2.18 (s, 3H)；13C NMR(101MHz,CDCl3)δ153.14, 152.96,139.90,139.82,139.66,136.27,133.44,129.45,128.33,127.67,127.64,127.56, 127.10,127.05,124.31,124.16,33.69,20.28.
Embodiment 6
The following 2,4- diphenyl -7- methyl -3-H-1,5- Benzodiazepine of preparation structure formula
In the present embodiment, the o-phenylenediamine used in equimolar 4- methyl-2-amino aniline alternative embodiment 1, His step is same as Example 1, obtains 2,4- diphenyl -7- methyl -3-H-1,5- Benzodiazepine, yield 99%, product Spectral data are as follows:1H NMR(400MHz,CDCl3) δ 8.01-7.94 (m, 4H), 7.53 (d, J=8.2Hz, 1H), 7.45- 7.43 (m, 1H), 7.43-7.40 (m, 5H), 7.18 (dd, J=8.3,2.0Hz, 1H), 2.48 (s, 3H)；13C NMR(101MHz, CDCl3)δ153.81,153.35,140.56,138.58,137.48,137.39,135.37,130.56,130.47,128.70, 128.68,128.61,128.14,128.09,126.93,35.03,21.17.
Embodiment 7
The following 2,4- diphenyl -6- methyl -3-H-1,5- Benzodiazepine of preparation structure formula
In the present embodiment, the o-phenylenediamine used in equimolar 3- methyl-2-amino aniline alternative embodiment 1, His step is same as Example 1, obtains 2,4- diphenyl -6- methyl -3-H-1,5- Benzodiazepine, yield 98%, product Spectral data are as follows:1H NMR(400MHz,CDCl3) δ 8.04 (dd, J=6.8,3.0Hz, 2H), 8.00 (dd, J=6.7, 3.1Hz,2H),7.54-7.48(m,1H),7.47-7.43(m,3H),7.43-7.38(m,3H),7.32-7.25(m,2H), 2.60(s,3H)；13C NMR(101MHz,CDCl3)δ153.87,151.79,140.49,139.13,137.47,136.33, 130.54,130.42,128.74,128.65,128.29,128.10,126.57,125.10,35.00,18.72.
Embodiment 8
The following bromo- 3-H-1,5- Benzodiazepine of 2,4- diphenyl -7,8- two of preparation structure formula
In the present embodiment, the o-phenylenediamine used in equimolar 4,5- dibromo o-phenylenediamine alternative embodiment 1, other Step is same as Example 1, obtains the bromo- 3-H-1 of 2,4- diphenyl -7,8- bis-, 5- Benzodiazepine, yield 96%, product Spectral data are as follows:1H NMR(400MHz,CDCl3)δ7.89-7.85(m,4H),7.79(s,2H),7.38-7.31(m,6H) ；13C NMR(101MHz,CDCl3)δ155.52,140.66,136.71,133.05,131.18,128.82,128.25, 120.58,35.16.
Embodiment 9
In the present embodiment, the M-phthalic acid used in equimolar 2- hydroxy niacin alternative embodiment 1, other steps It is same as Example 1, obtain 2,4- diphenyl -3-H-1,5- Benzodiazepine, yield 86%.
Embodiment 10
In the present embodiment, the M-phthalic acid used in equimolar salicylic acid alternative embodiment 1, other steps and reality It is identical to apply example 1, obtains 2,4- diphenyl -3-H-1,5- Benzodiazepine, yield 81%.
Embodiment 11
In the present embodiment, the ethyl alcohol used in isometric methanol alternative embodiment 1, other steps and 1 phase of embodiment Together, 2,4- diphenyl -3-H-1,5- Benzodiazepine, yield 87% are obtained.

Claims (7)

1. a kind of method that cyclopentadienyl titanium dichloride catalysis prepares benzodiazepine compound, it is characterised in that: by 3- fourth shown in Formulas I O-phenylenediamine class compound shown in alkynes -2- ketone compounds and Formula II is added in organic solvent, and cyclopentadienyl titanium dichloride is added and matches Body reacts 6~24 hours at room temperature, isolates and purifies product, obtain benzodiazepine compound shown in formula III；
R in formula1And R2Aryl or substituted aryl independent；R3、R4、R5、R6It is independent to represent H, C1~C4Alkyl, C1 ~C4Any one in alkoxy, F, Cl, Br；
Above-mentioned organic solvent is ethyl alcohol, any one in methanol；
Above-mentioned ligand is M-phthalic acid, 2- hydroxy niacin, any one in salicylic acid.
2. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 prepares benzodiazepine compound, it is characterised in that: The R1And R2It is independent to represent phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Alkoxy substituted phenyl, halogeno-benzene Base, trifluoromethyl substituted-phenyl, any one in nitro substituted-phenyl.
3. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 or 2 prepares benzodiazepine compound, feature exist In: the organic solvent is ethyl alcohol.
4. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 or 2 prepares benzodiazepine compound, feature exist In: the ligand is M-phthalic acid.
5. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 or 2 prepares benzodiazepine compound, feature exist In: the molar ratio of the 3- crotonylene -one class compound and o-phenylenediamine class compound is 1:1.1~1.5.
6. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 or 2 prepares benzodiazepine compound, feature exist In: the additional amount of the cyclopentadienyl titanium dichloride is the 1%~3% of 3- crotonylene -one class compound mole.
7. the method that cyclopentadienyl titanium dichloride catalysis according to claim 1 or 2 prepares benzodiazepine compound, feature exist In: the additional amount of the ligand is the 2%~6% of 3- crotonylene -one class compound mole.
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CN112812070A (en) * 2021-01-30 2021-05-18 陕西师范大学 Method for preparing benzodiazepine compound by high-efficiency catalysis of palladium pyridine

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CN112812070A (en) * 2021-01-30 2021-05-18 陕西师范大学 Method for preparing benzodiazepine compound by high-efficiency catalysis of palladium pyridine
CN112812070B (en) * 2021-01-30 2022-10-21 陕西师范大学 Method for preparing benzodiazepine compound by high-efficiency catalysis of palladium pyridine

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