CN103396436A - Monobutyltin trichloride substituted salicylidenedimine Schiff base complex as well as preparation method and applications thereof - Google Patents
Monobutyltin trichloride substituted salicylidenedimine Schiff base complex as well as preparation method and applications thereof Download PDFInfo
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- CN103396436A CN103396436A CN2013103084095A CN201310308409A CN103396436A CN 103396436 A CN103396436 A CN 103396436A CN 2013103084095 A CN2013103084095 A CN 2013103084095A CN 201310308409 A CN201310308409 A CN 201310308409A CN 103396436 A CN103396436 A CN 103396436A
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- monobutyltin
- schiff alkali
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- substituted salicylic
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- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical group CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 150000004753 Schiff bases Chemical class 0.000 title abstract description 6
- 239000002262 Schiff base Substances 0.000 title abstract 4
- 238000010668 complexation reaction Methods 0.000 title description 3
- -1 R1 is -H Chemical group 0.000 claims abstract description 39
- 239000003814 drug Substances 0.000 claims abstract description 19
- 206010028980 Neoplasm Diseases 0.000 claims abstract 3
- 239000003513 alkali Substances 0.000 claims description 134
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 68
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical group CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 63
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 48
- 150000001299 aldehydes Chemical class 0.000 claims description 48
- 150000004982 aromatic amines Chemical class 0.000 claims description 48
- 238000002447 crystallographic data Methods 0.000 claims description 30
- 125000006850 spacer group Chemical group 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 206010009944 Colon cancer Diseases 0.000 claims description 9
- 201000007270 liver cancer Diseases 0.000 claims description 9
- 208000014018 liver neoplasm Diseases 0.000 claims description 9
- 206010006187 Breast cancer Diseases 0.000 claims description 8
- 208000026310 Breast neoplasm Diseases 0.000 claims description 8
- 206010058467 Lung neoplasm malignant Diseases 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 201000005202 lung cancer Diseases 0.000 claims description 4
- 208000020816 lung neoplasm Diseases 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 206010008342 Cervix carcinoma Diseases 0.000 claims description 3
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 claims description 3
- 201000010881 cervical cancer Diseases 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229940079593 drug Drugs 0.000 abstract description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 33
- 238000004458 analytical method Methods 0.000 description 22
- 229910020813 Sn-C Inorganic materials 0.000 description 21
- 229910018732 Sn—C Inorganic materials 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 229910020923 Sn-O Inorganic materials 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000259 anti-tumor effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000011275 oncology therapy Methods 0.000 description 6
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 125000006416 CBr Chemical group BrC* 0.000 description 4
- 125000006414 CCl Chemical group ClC* 0.000 description 4
- 208000019065 cervical carcinoma Diseases 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002246 antineoplastic agent Substances 0.000 description 3
- 229940041181 antineoplastic drug Drugs 0.000 description 3
- 208000029742 colonic neoplasm Diseases 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 201000005296 lung carcinoma Diseases 0.000 description 3
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 3
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 2
- 208000001333 Colorectal Neoplasms Diseases 0.000 description 2
- 208000002454 Nasopharyngeal Carcinoma Diseases 0.000 description 2
- 206010061306 Nasopharyngeal cancer Diseases 0.000 description 2
- 208000005718 Stomach Neoplasms Diseases 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 201000010989 colorectal carcinoma Diseases 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 2
- 201000011216 nasopharynx carcinoma Diseases 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 201000000498 stomach carcinoma Diseases 0.000 description 2
- JHZOXYGFQMROFJ-UHFFFAOYSA-N 3,5-dibromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=C(Br)C=C1C=O JHZOXYGFQMROFJ-UHFFFAOYSA-N 0.000 description 1
- AZKSAVLVSZKNRD-UHFFFAOYSA-M 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide Chemical compound [Br-].S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 AZKSAVLVSZKNRD-UHFFFAOYSA-M 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 201000008275 breast carcinoma Diseases 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical class CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 238000003255 drug test Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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Abstract
The invention discloses a monobutyltin trichloride substituted salicylidenedimine Schiff base complex which is a complex with the following structural formula (I), wherein Bu represents n-butyl, R1 is -H, -Cl or -Br, R2 is -H or -N(CH2CH3)2, R3 is -H, -Cl or -Br, and R4 is -H, -Cl, -NO2 or -Me. The invention further discloses a preparation method of the monobutyltin trichloride substituted salicylidenedimine Schiff base complex, and applications of the monobutyltin trichloride substituted salicylidenedimine Schiff base complex in drugs for treating tumor.
Description
Technical field
The present invention relates to serial Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex and preparation method and application, and preparation method thereof, and should the application of series title complex in preparing antitumor drug.
Background technology
Schiff alkali is the compound that a class has pharmacology and physiologically active, because it is take nitrogen-atoms and Sauerstoffatom as ligating atom, comparatively approaching with coenocorrelation, it is the focus that people study always, 3 of series, 5-diiodo-salicylic aldehyde Schiff alkali and the application in preparing antiseptic-germicide thereof are disclosed as Chinese patent CN101302172.
Organotin is the organometallics that a class contains the Sn-C key, has the compound than high biological activity, in sterilization, cancer therapy drug preparation, has wide practical use.Already studied and showed, radicals R and playing an important role with the structure of the part of the tin atom coordination antitumour activity to compound in organotin, as, the antitumour activity of cyclohexyl, normal-butyl and phenyltin compound is stronger, and ethyl takes second place, and methyl is almost without anticancer activity.Before experiment showed, biological activity ratio's coordination of Schiff bases part after forming title complex, obviously strengthen, its title complex has biological and pharmacoligical activities widely.Therefore, Schiff bases part is combined with organotin, becomes a research direction of people's interest.
A kind of dibutyl tin dichloride Schiff alkali coordination compound and the application in preparation treatment cancer of the stomach, nasopharyngeal carcinoma, people's liver cancer or leukemic medicine thereof are disclosed as Chinese patent CN101475583.
Chinese patent CN102718794A discloses a kind of pair of acylhydrazone class Schiff alkali tin diphenyl (IV) title complex and the application in preparation treatment adenocarcinoma of lung, colorectal carcinoma, leukemia cell's medicine thereof.
Chinese patent CN101434616 discloses a kind of organotin Schiff alkali coordination compound and the application in preparation treatment cancer of the stomach, nasopharyngeal carcinoma, people's liver cancer or leukemic medicine thereof.
Chinese patent CN101851251A discloses a kind of dibutyl tin (IV) title complex and application in preparing Hepatoma therapy, adenocarcinoma of lung, mammary cancer, prostate cancer, colorectal carcinoma or the leukemic medicine of children's grain morning thereof of acylhydrazone class Schiff aar ligand.
based on the butyl tin compounds, be to the experiment proved that the material with antitumour activity, the present invention selects the organo-tin compound of monobutyl tin trichloride, respectively with 3, the 5-dichloro-salicylaldehyde, the 5-bromosalicylaldehyde, 4-(diethylin) salicylic aldehyde and 3, substituted salicylic aldehydes and the 4-chlorine o-aminophenols such as 5-Dibromosalicylaldehyde, 4-nitro o-aminophenol, the Schiff alkali of the arylamine condensations such as o-aminophenol and 4-methyl o-aminophenol is part, reaction under certain condition, synthetic having obtained human cervical carcinoma cell (Hela), human breast cancer cell (MCF7), human liver cancer cell (HepG2), human colon cancer cell (Colo205), the stronger compound of inhibition activity of human lung carcinoma cell (NCI-H460), for the exploitation cancer therapy drug provides new way.
Summary of the invention
One of purpose of the present invention is to provide serial Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex.
Two of the object of the invention is to provide the preparation method of above-mentioned serial Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex.
Three of the object of the invention is to provide the application of above-mentioned serial Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex in medicine.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex is the title complex of following structural formula (I):
Wherein Bu represents normal-butyl, R
1For-H ,-Cl or-Br, R
2For-H or-N (CH
2CH
3)
2, R
3For-H ,-Cl or-Br, R
4For-H ,-Cl ,-NO
2Or-Me.
In a preferred embodiment of the invention, work as R
1For-Cl, R
2For-H, R
3For-Cl, R
4During for-Cl, structural formula (I) is in title complex (I-1).
In a preferred embodiment of the invention, described title complex (I-1) is crystalline structure.
In a preferred embodiment of the invention, the crystallographic data of described title complex (I-1): oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
In a preferred embodiment of the invention, work as R
1For-H, R
2For-H, R
3For-Br, R
4For-NO
2The time, structural formula (I) is in title complex (I-2).
In a preferred embodiment of the invention, described title complex (I-2) is crystalline structure.
In a preferred embodiment of the invention, the crystallographic data of described title complex (I-2): triclinic(crystalline)system, spacer
, a=0.88989 (2) nm, b=1.14166 (3) nm, c=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
In a preferred embodiment of the invention, work as R
1For-Cl, R
2For-H, R
3For-Cl, R
4During for-H, structural formula (I) is in title complex (I-3).
In a preferred embodiment of the invention, described title complex (I-3) is crystalline structure.
In a preferred embodiment of the invention, the crystallographic data of described title complex (I-3): oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
In a preferred embodiment of the invention, work as R
1For-H, R
2For-N (CH
2CH
3)
2, R
3For-H, R
4For-NO
2The time, structural formula (I) is in title complex (I-4).
In a preferred embodiment of the invention, described title complex (I-4) is crystalline structure.
In a preferred embodiment of the invention, the crystallographic data of described title complex (I-4): oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
In a preferred embodiment of the invention, work as R
1For-Br, R
2For-H, R
3For-Br, R
4During for-Me, structural formula (I) is in title complex (I-5).
In a preferred embodiment of the invention, described title complex (I-5) is crystalline structure.
In a preferred embodiment of the invention, the crystallographic data of described title complex (I-5): oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
The preparation method of Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex of the present invention, be in reaction vessel, to add successively in order substituted salicylic aldehydes contracting arylamine Schiff alkali, monobutyl tin trichloride, sodium methylate and solvent anhydrous methanol, under stirring and refluxing, react 8～12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex;
Wherein substituted salicylic aldehydes contracting arylamine Schiff alkali, monobutyl tin trichloride are reactant, sodium methylate is catalyzer, anhydrous methanol is reaction solvent, reactant substituted salicylic aldehydes contracting arylamine Schiff alkali is 1:1～1:1.05 with the amount of substance ratio of monobutyl tin trichloride, the catalyzer sodium methylate is 0.004:1～0.05:1 with the amount of substance ratio of reactant substituted salicylic aldehydes contracting arylamine Schiff alkali, and the consumption of solvent anhydrous methanol is that every mmole monobutyl tin trichloride adds 30～55 ml methanol.
The applicant has carried out anti tumor activity in vitro to above-mentioned Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex and has confirmed research, confirm that this Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex has anti-tumor biological, the purposes that is to say above-mentioned Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex is the application in preparing antitumor drug, is exactly specifically the application in preparing anti-cervical cancer or anti-breast cancer or anti-liver cancer or inhibitor against colon carcinoma cells or anti-lung-cancer medicament.
Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex of the present invention has antitumour activity preferably, can it for raw material, prepare anti-cervical cancer, anti-breast cancer, anti-liver cancer, inhibitor against colon carcinoma cells, anti-lung-cancer medicament.With the platinum-containing anticancer drug that generally uses at present, compare, Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex of the present invention has the characteristics such as antitumour activity is high, cost is low, the preparation method is simple, for the exploitation cancer therapy drug provides new way.
The accompanying drawing explanation
Fig. 1 is Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-1) crystal molecule structure iron.
Fig. 2 is Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-2) crystal molecule structure iron.
Fig. 3 is Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-3) crystal molecule structure iron.
Fig. 4 is Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-4) crystal molecule structure iron.
Fig. 5 is Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-5) crystal molecule structure iron.
Embodiment
By following examples, further describe the present invention, but should notice that scope of the present invention is not subjected to any restriction of these embodiment.
Embodiment 1:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali 0.158g (0.5mmol), monobutyl tin trichloride 0.141g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1).Productive rate: 82%, fusing point: 149～152 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1) ultimate analysis (C
, 18H
19Cl
4N
1O
3Sn): theoretical value: C, 38.75, H, 3.43, N, 2.51; Measured value: C, 38.71, H, 3.53, N, 2.42.
IR(KBr,cm
-1):2958,2927ν(C-H),1605,1527ν(C=N),1185ν(C-O),546ν(Sn-O),440ν(Sn-N),415ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.90(s,1H,H-3),7.73(s,1H,H-5),9.23(s,1H,H-7),7.79(d,J=2.0Hz,1H,H-9),6.87(dd,J
1=8.4Hz,J
2=2.0Hz,1H,H-11),7.20(d,J=8.4Hz,1H,H-12),4.09(s,1H,CH
3OH),3.17(s,3H,CH
3OH),1.45-1.62(m,4H,?H-α,H-γ),1.78(q,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),159.50(C-7),13.46(C-θ),25.05(C-α),26.71(C-γ),27.54(C-β),116.19,119.59,119.63,119.65,120.46,126.02,129.81,130.14,132.95,133.85,155.01,160.53(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3, D
c=1.688Mgm
-3, μ (MoK
α)=1.669mm
-1, F (000)=2208,1.76 °<θ<27.50 °, crystalline size: 0.19 * 0.17 * 0.13mm, R=0.0501, wR=0.1384.
Embodiment 2:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali 0.633g (2.0mmol), monobutyl tin trichloride 0.587g (2.08mmol), sodium methylate 0.005g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1).Productive rate: 74%, fusing point: 149～152 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1) ultimate analysis (C
, 18H
19Cl
4N
1O
3Sn): theoretical value: C, 38.75, H, 3.43, N, 2.51; Measured value: C, 38.71, H, 3.53, N, 2.42.
IR(KBr,cm
-1):2958,2927ν(C-H),1605,1527ν(C=N),1185ν(C-O),546ν(Sn-O),440ν(Sn-N),415ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.90(s,1H,H-3),7.73(s,1H,H-5),9.23(s,1H,H-7),7.79(d,J=2.0Hz,1H,H-9),6.87(dd,J
1=8.4Hz,J
2=2.0Hz,1H,H-11),7.20(d,J=8.4Hz,1H,H-12),4.09(s,1H,CH
3OH),3.17(s,3H,CH
3OH),1.45-1.62(m,4H,?H-α,H-γ),1.78(q,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),159.50(C-7),13.46(C-θ),25.05(C-α),26.71(C-γ),27.54(C-β),116.19,119.59,119.63,119.65,120.46,126.02,129.81,130.14,132.95,133.85,155.01,160.53(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3, D
c=1.688Mgm
-3, μ (MoK
α)=1.669mm
-1, F (000)=2208,1.76 °<θ<27.50 °, crystalline size: 0.19 * 0.17 * 0.13mm, R=0.0501, wR=0.1384.
Embodiment 3:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali 0.317g (1.0mmol), monobutyl tin trichloride 0.288g (1.02mmol), sodium methylate 0.0005g (0.01mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (1).Productive rate: 73%, fusing point: 149～152 ℃.
Ultimate analysis (C
18H
19Cl
4N
1O
3Sn): theoretical value: C, 38.75, H, 3.43, N, 2.51; Measured value: C, 38.71, H, 3.53, N, 2.42.
IR(KBr,cm
-1):2958,2927ν(C-H),1605,1527ν(C=N),1185ν(C-O),546ν(Sn-O),440ν(Sn-N),415ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.90(s,1H,H-3),7.73(s,1H,H-5),9.23(s,1H,H-7),7.79(d,J=2.0Hz,1H,H-9),6.87(dd,J
1=8.4Hz,J
2=2.0Hz,1H,H-11),7.20(d,J=8.4Hz,1H,H-12),4.09(s,1H,CH
3OH),3.17(s,3H,CH
3OH),1.45-1.62(m,4H,H-α,H-γ),1.78(q,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,?3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),159.50(C-7),13.46(C-θ),25.05(C-α),26.71(C-γ),27.54(C-β),116.19,119.59,119.63,119.65,120.46,126.02,129.81,130.14,132.95,133.85,155.01,160.53(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3, D
c=1.688Mgm
-3, μ (MoK
α)=1.669mm
-1, F (000)=2208,1.76 °<θ<27.50 °, crystalline size: 0.19 * 0.17 * 0.13mm, R=0.0501, wR=0.1384.
Embodiment 4:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali 0.475g (1.5mmol), monobutyl tin trichloride 0.444g (1.575mmol), sodium methylate 0.0016g (0.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1).Productive rate: 78%, fusing point: 149～152 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex (I-1) ultimate analysis (C
, 18H
19Cl
4N
1O
3Sn): theoretical value: C, 38.75, H, 3.43, N, 2.51; Measured value: C, 38.71, H, 3.53, N, 2.42.
IR(KBr,cm
-1):2958,2927ν(C-H),1605,1527ν(C=N),1185ν(C-O),546ν(Sn-O),440ν(Sn-N),415ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.90(s,1H,H-3),7.73(s,1H,H-5),9.23(s,1H,H-7),7.79(d,J=2.0Hz,1H,H-9),6.87(dd,J
1=8.4Hz,J
2=2.0Hz,1H,H-11),7.20(d,J=8.4Hz,1H,H-12),4.09(s,1H,CH
3OH),3.17(s,3H,CH
3OH),1.45-1.62(m,4H,H-α,H-γ),1.78(q,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,?3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),159.50(C-7),13.46(C-θ),25.05(C-α),26.71(C-γ),27.54(C-β),116.19,119.59,119.63,119.65,120.46,126.02,129.81,130.14,132.95,133.85,155.01,160.53(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3, D
c=1.688Mgm
-3, μ (MoK
α)=1.669mm
-1, F (000)=2208,1.76 °<θ<27.50 °, crystalline size: 0.19 * 0.17 * 0.13mm, R=0.0501, wR=0.1384.
Embodiment 5:
The preparation of Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.169g (0.5mmol), monobutyl tin trichloride 0.141g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 82%, fusing point: 268～269 ℃.
Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2) ultimate analysis (C
19H
24BrClN
2O
6Sn): theoretical value: C, 37.38, H, 3.96, N, 4.59; Measured value: C, 37.33, H, 3.93, N, 4.61.
IR(KBr,cm
-1):2958,2925ν(C-H),1610,1592ν(C=N),1158ν(C-O),548ν(Sn-O),436ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.82(d,J=8.8Hz,1H,H-2),7.60(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.98(d,J=1.8Hz,1H,H-5),9.43(s,1H,H-7),8.80(d,J=1.8Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.98(d,J=8.8Hz,1H,H-12),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,?CH
3OH),1.57(t,J=8.0Hz,2H,H-α),1.75(quint,J=7.2Hz,2H,H-β),1.45(sext,J=7.2Hz,2H,H-γ),0.94(t,J=7.6Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),161.86(C-7),13.40(C-θ),25.07(C-α),26.81(C-γ),27.56(C-β),107.72,112.88,118.05,119.70,124.42,125.39,129.44,137.21,137.53,138.50,162.25,166.59(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer
, a=0.88989 (2) nm, b=1.14166 (3) nm,
C=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3, D
c=1.747Mgm-
3, μ (MoK
α)=2.974mm
-1, F (000)=604,2.41 °<θ<27.58 °, crystalline size: 0.28 * 0.26 * 0.22mm, R=0.0394, wR=0.1032.
Embodiment 6:
The preparation of Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.674g (2.0mmol), monobutyl tin trichloride 0.587g (2.08mmol), sodium methylate 0.005g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 84%, fusing point: 268～269 ℃.
Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2) ultimate analysis (C
19H
24BrClN
2O
6Sn): theoretical value: C, 37.38, H, 3.96, N, 4.59; Measured value: C, 37.33, H, 3.93, N, 4.61.
IR(KBr,cm
-1):2958,2925ν(C-H),1610,1592ν(C=N),1158ν(C-O),548ν(Sn-O),436ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.82(d,J=8.8Hz,1H,H-2),7.60(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.98(d,J=1.8Hz,?1H,H-5),9.43(s,1H,H-7),8.80(d,J=1.8Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.98(d,J=8.8Hz,1H,H-12),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.57(t,J=8.0Hz,2H,H-α),1.75(quint,J=7.2Hz,2H,H-β),1.45(sext,J=7.2Hz,2H,H-γ),0.94(t,J=7.6Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),161.86(C-7),13.40(C-θ),25.07(C-α),26.81(C-γ),27.56(C-β),107.72,112.88,118.05,119.70,124.42,125.39,129.44,137.21,137.53,138.50,162.25,166.59(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer
, a=0.88989 (2) nm, b=1.14166 (3) nm,
C=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3, D
c=1.747Mgm
-3, μ (MoK
α)=2.974mm
-1, F (000)=604,2.41 °<θ<27.58 °, crystalline size: 0.28 * 0.26 * 0.22mm, R=0.0394, wR=0.1032.
Embodiment 7:
The preparation of Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.337g (1.0mmol), monobutyl tin trichloride 0.288g (1.02mmol), sodium methylate 0.001g (0.02mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 83%, fusing point: 268～269 ℃.
Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2) ultimate analysis (C
19H
24BrClN
2O
6Sn): theoretical value: C, 37.38, H, 3.96, N, 4.59; Measured value: C, 37.33, H, 3.93, N, 4.61.
IR(KBr,cm
-1):2958,2925ν(C-H),1610,1592ν(C=N),?1158ν(C-O),548ν(Sn-O),436ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.82(d,J=8.8Hz,1H,H-2),7.60(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.98(d,J=1.8Hz,1H,H-5),9.43(s,1H,H-7),8.80(d,J=1.8Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.98(d,J=8.8Hz,1H,H-12),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.57(t,J=8.0Hz,2H,H-α),1.75(quint,J=7.2Hz,2H,H-β),1.45(sext,J=7.2Hz,2H,H-γ),0.94(t,J=7.6Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),161.86(C-7),13.40(C-θ),25.07(C-α),26.81(C-γ),27.56(C-β),107.72,112.88,118.05,119.70,124.42,125.39,129.44,137.21,137.53,138.50,162.25,166.59(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer
, a=0.88989 (2) nm, b=1.14166 (3) nm,
C=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3, D
c=1.747Mgm
-3, μ (MoK
α)=2.974mm
-1, F (000)=604,2.41 °<θ<27.58 °, crystalline size: 0.28 * 0.26 * 0.22mm, R=0.0394, wR=0.1032.
Embodiment 8:
The preparation of Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.506g (1.5mmol), monobutyl tin trichloride 0.444g (1.575mmol), sodium methylate 0.002g (0.04mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 78%, fusing point: 268～269 ℃.
Monobutyltin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2) ultimate analysis (C
19H
24BrClN
2O
6Sn): theoretical value: C, 37.38, H, 3.96, N, 4.59; Measured value: C, 37.33, H, 3.93, N, 4.61.
IR(KBr,cm
-1):2958,2925ν(C-H),1610,1592ν(C=N),1158ν(C-O),548ν(Sn-O),436ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.82(d,J=8.8Hz,1H,H-2),7.60(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.98(d,J=1.8Hz,1H,H-5),9.43(s,1H,H-7),8.80(d,J=1.8Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.98(d,J=8.8Hz,1H,H-12),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.57(t,J=8.0Hz,2H,H-α),1.75(quint,J=7.2Hz,2H,H-β),1.45(sext,J=7.2Hz,2H,H-γ),0.94(t,J=7.6Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),161.86(C-7),13.40(C-θ),25.07(C-α),26.81(C-γ),27.56(C-β),107.72,112.88,118.05,119.70,124.42,125.39,129.44,137.21,137.53,138.50,162.25,166.59(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer
, a=0.88989 (2) nm, b=1.14166 (3) nm,
C=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3, D
c=1.747Mgm
-3, μ (MoK
α)=2.974mm
-1, F (000)=604,2.41 °<θ<27.58 °, crystalline size: 0.28 * 0.26 * 0.22mm, R=0.0394, wR=0.1032.
Embodiment 9:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali 0.141g (0.5mmol), monobutyl tin trichloride 0.141g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the deep yellow crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3).Productive rate: 80%, fusing point: 262～263 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3) ultimate analysis (C
18H
20Cl
3NO
3Sn): theoretical value: C, 41.30, H, 3.85, N, 2.68; Measured value: C, 41.35, H, 3.75, N, 2.74.
IR(KBr,cm
-1):2952,2926ν(C-H),1607,1592ν(C=N),1256ν(C-O),1115ν(C-Cl),544ν(Sn-O),496ν(Sn-N),426ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.75-7.77(m,3H,H-3,H-9,H-12),6.84(d,J=7.6Hz,1H,H-5),9.18(s,1H,H-7),6.79(t,J=7.6Hz,1H,H-10),7.24(t,J=7.6Hz,1H,H-11),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.45-1.58(m,4H,H-α,H-γ),1.80(quint,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):49.11(CH
3OH),158.60(C-7),14.17(C-θ),25.79(C-α),27.46(C-γ),28.12(C-β),116.76,117.53,118.99,120.19,120.49,126.62,129.99,131.10,133.38,134.08,156.91,161.04(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3, D
c=1.642Mgm
-3, μ (MoK
α)=1.603mm
-1, F (000)=2080,2.31 °<θ<27.51 °, crystalline size: 0.31 * 0.24 * 0.19mm, R=0.0269, wR=0.0734.
Embodiment 10:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali 0.564g (2.0mmol), monobutyl tin trichloride 0.587g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the deep yellow crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3).Productive rate: 82%, fusing point: 262～263 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3) ultimate analysis (C
18H
20Cl
3NO
3Sn): theoretical value: C, 41.30, H, 3.85, N, 2.68; Measured value: C, 41.35, H, 3.75, N, 2.74.
IR(KBr,cm
-1):2952,2926ν(C-H),1607,1592ν(C=N),1256ν(C-O),1115ν(C-Cl),544ν(Sn-O),496ν(Sn-N),426ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.75-7.77(m,3H,H-3,H-9,H-12),6.84(d,J=7.6Hz,1H,H-5),9.18(s,1H,H-7),6.79(t,J=7.6Hz,1H,H-10),7.24(t,J=7.6Hz,1H,H-11),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.45-1.58(m,4H,H-α,H-γ),1.80(quint,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):49.11(CH
3OH),158.60(C-7),14.17(C-θ),25.79(C-α),27.46(C-γ),28.12(C-β),116.76,117.53,118.99,120.19,120.49,126.62,129.99,131.10,133.38,134.08,156.91,161.04(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3, D
c=1.642Mgm
-3, μ (MoK
α)=1.603mm
-1, F (000)=2080,2.31 °<θ<27.51 °, crystalline size: 0.31 * 0.24 * 0.19mm, R=0.0269, wR=0.0734.
Embodiment 11:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali 0.288g (1.0mmol), monobutyl tin trichloride 0.288g (1.02mmol), sodium methylate 0.0005g (0.01mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the deep yellow crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3).Productive rate: 73%, fusing point: 262～263 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3) ultimate analysis (C
18H
20Cl
3NO
3Sn): theoretical value: C, 41.30, H, 3.85, N, 2.68; Measured value: C, 41.35, H, 3.75, N, 2.74.
IR(KBr,cm
-1):2952,2926ν(C-H),1607,1592ν(C=N),1256ν(C-O),1115ν(C-Cl),544ν(Sn-O),496ν(Sn-N),426ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.75-7.77(m,3H,H-3,H-9,H-12),6.84(d,J=7.6Hz,1H,H-5),9.18(s,1H,H-7),6.79(t,J=7.6Hz,1H,H-10),7.24(t,J=7.6Hz,1H,H-11),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.45-1.58(m,4H,H-α,H-γ),1.80(quint,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):49.11(CH
3OH),158.60(C-7),14.17(C-θ),25.79(C-α),27.46(C-γ),28.12(C-β),116.76,117.53,118.99,120.19,120.49,126.62,129.99,131.10,133.38,134.08,156.91,161.04(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3, D
c=1.642Mgm
-3, μ (MoK
α)=1.603mm
-1, F (000)=2080,2.31 °<θ<27.51 °, crystalline size: 0.31 * 0.24 * 0.19mm, R=0.0269, wR=0.0734.
Embodiment 12:
Monobutyltin 3, the preparation of 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali 0.423g (1.5mmol), monobutyl tin trichloride 0.444g (1.575mmol), sodium methylate 0.0016g (0.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the deep yellow crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3).Productive rate: 78%, fusing point: 262～263 ℃.
Monobutyltin 3,5-dichloro-salicylaldehyde contracting o-aminophenol Schiff alkali title complex (I-3) ultimate analysis (C
18H
20Cl
3NO
3Sn): theoretical value: C, 41.30, H, 3.85, N, 2.68; Measured value: C, 41.35, H, 3.75, N, 2.74.
IR(KBr,cm
-1):2952,2926ν(C-H),1607,1592ν(C=N),1256ν(C-O),1115ν(C-Cl),544ν(Sn-O),496ν(Sn-N),426ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.75-7.77(m,3H,H-3,H-9,H-12),6.84(d,J=7.6Hz,1H,H-5),9.18(s,1H,H-7),6.79(t,J=7.6Hz,1H,H-10),7.24(t,J=7.6Hz,1H,H-11),4.08(q,J=5.2Hz,2H,CH
3OH),3.17(d,J=5.2Hz,6H,CH
3OH),1.45-1.58(m,4H,H-α,H-γ),1.80(quint,J=7.2Hz,2H,H-β),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):49.11(CH
3OH),158.60(C-7),14.17(C-θ),25.79(C-α),27.46(C-γ),28.12(C-β),116.76,117.53,118.99,120.19,120.49,126.62,129.99,131.10,133.38,134.08,156.91,161.04(Ar-C)。
Crystallographic data: oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3, D
c=1.642Mgm
-3, μ (MoK
α)=1.603mm
-1, F (000)=2080,2.31 °<θ<27.51 °, crystalline size: 0.31 * 0.24 * 0.19mm, R=0.0269, wR=0.0734.
Embodiment 13:
The preparation of Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4):
In round-bottomed flask, add successively in order 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali 0.165g (0.5mmol), monobutyl tin trichloride 0.141g (0.5mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the scarlet crystal, be Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 83%, fusing point: 238～240 ℃.
Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4) ultimate analysis (C
22H
30ClN
3O
5Sn): theoretical value: C, 46.30, H, 5.30, N, 7.36; Measured value: C, 46.34, H, 5.35, N, 7.31.
IR(KBr,cm
-1):2971,2957ν(C-H),1617,1576ν(C=N),1528ν(C-NO
2),1356ν(C-N),1249ν(C-O),612ν(Sn-O),514ν(Sn-N),419ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):5.92(d,J=2.0Hz,1H,H-2),6.41(dd,J
1=2.0Hz,J
2=8.8Hz,1H,H-4),6.85(d,J=8.8Hz,1H,H-5),8.96(s,1H,H-7),8.55(d,J=2.0Hz,1H,H-9),7.97(dd,J
1=2.0Hz,J
2=9.2Hz,1H,H-11),7.48(d,J=9.2Hz,1H,H-12),3.45(q,J=6.8Hz,4H,-N(CH
2CH
3)
2),3.17(s,3H,CH
3OH),1.40-1.76(m,6H,H-α,H-β,H-γ),1.15(t,J=6.8Hz,6H,-N(CH
2CH
3)
2),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),157.78(C-7),43.97(-N(CH
2CH
3)
2),12.58(-N(CH
2CH
3)
2),13.43(C-θ),25.25(C-α),26.97(C-γ),28.06(C-β),99.97,105.17,109.37,110.09,116.53,122.77,131.22,136.74,138.37,154.54,161.84,169.89(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3, D
c=1.494Mgm
-3, μ (MoK
α)=1.148mm
-1, F (000)=1160,2.30 °<θ<25.00 °, crystalline size: 0.31 * 0.29 * 0.27mm, R=0.0499, wR=0.1311.
Embodiment 14:
The preparation of Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4):
In round-bottomed flask, add successively in order 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali 0.659g (2.0mmol), monobutyl tin trichloride 0.587g (2.08mmol), sodium methylate 0.005g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the scarlet crystal, be Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 84%, fusing point: 238～240 ℃.
Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4) ultimate analysis (C
22H
30ClN
3O
5Sn): theoretical value: C, 46.30, H, 5.30, N, 7.36; Measured value: C, 46.34, H, 5.35, N, 7.31.
IR(KBr,cm
-1):2971,2957ν(C-H),1617,1576ν(C=N),1528ν(C-NO
2),1356ν(C-N),1249ν(C-O),612ν(Sn-O),514ν(Sn-N),419ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):5.92(d,J=2.0Hz,1H,H-2),6.41(dd,J
1=2.0Hz,J
2=8.8Hz,1H,H-4),6.85(d,J=8.8Hz,1H,H-5),8.96(s,1H,H-7),8.55(d,J=2.0Hz,1H,H-9),7.97(dd,J
1=2.0Hz,J
2=9.2Hz,1H,H-11),7.48(d,J=9.2Hz,1H,H-12),3.45(q,J=6.8Hz,4H,-N(CH
2CH
3)
2),3.17(s,3H,CH
3OH),1.40-1.76(m,6H,H-α,H-β,H-γ),1.15(t,J=6.8Hz,6H,-N(CH
2CH
3)
2),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),157.78(C-7),43.97(-N(CH
2CH
3)
2),12.58(-N(CH
2CH
3)
2),13.43(C-θ),25.25(C-α),26.97(C-γ),28.06(C-β),99.97,105.17,109.37,110.09,116.53,122.77,131.22,136.74,138.37,154.54,161.84,169.89(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3, D
c=1.494Mgm
-3, μ (MoK
α)=1.148mm
-1, F (000)=1160,2.30 °<θ<25.00 °, crystalline size: 0.31 * 0.29 * 0.27mm, R=0.0499, wR=0.1311.
Embodiment 15:
The preparation of Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4):
In round-bottomed flask, add successively in order 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali 0.329g (1.0mmol), monobutyl tin trichloride 0.288g (1.02mmol), sodium methylate 0.0005g (0.01mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the scarlet crystal, be Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 80%, fusing point: 238～240 ℃.
Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4) ultimate analysis (C
22H
30ClN
3O
5Sn): theoretical value: C, 46.30, H, 5.30, N, 7.36; Measured value: C, 46.34, H, 5.35, N, 7.31.
IR(KBr,cm
-1):2971,2957ν(C-H),1617,1576ν(C=N),1528ν(C-NO
2),1356ν(C-N),1249ν(C-O),612ν(Sn-O),514ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):5.92(d,J=2.0Hz,1H,H-2),6.41(dd,J
1=2.0Hz,J
2=8.8Hz,1H,H-4),6.85(d,J=8.8Hz,1H,H-5),8.96(s,1H,H-7),8.55(d,J=2.0Hz,1H,H-9),7.97(dd,J
1=2.0Hz,J
2=9.2Hz,1H,H-11),7.48(d,J=9.2Hz,1H,H-12),3.45(q,J=6.8Hz,4H,-N(CH
2CH
3)
2),3.17(s,3H,CH
3OH),1.40-1.76(m,6H,H-α,H-β,H-γ),1.15(t,J=6.8Hz,6H,-N(CH
2CH
3)
2),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),157.78(C-7),43.97(-N(CH
2CH
3)
2),12.58(-N(CH
2CH
3)
2),13.43(C-θ),25.25(C-α),26.97(C-γ),28.06(C-β),99.97,105.17,109.37,110.09,116.53,122.77,131.22,136.74,138.37,154.54,161.84,169.89(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3, D
c=1.494Mgm
-3, μ (MoK
α)=1.148mm
-1, F (000)=1160,2.30 °<θ<25.00 °, crystalline size: 0.31 * 0.29 * 0.27mm, R=0.0499, wR=0.1311.
Embodiment 16:
The preparation of Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4):
In round-bottomed flask, add successively in order 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali 0.494g (1.5mmol), monobutyl tin trichloride 0.444g (1.575mmol), sodium methylate 0.0016g (0.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the scarlet crystal, be Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 79%, fusing point: 238～240 ℃.
Monobutyltin 4-(diethylin) salicylidene 4-nitro o-aminophenol Schiff alkali title complex (I-4) ultimate analysis (C
22H
30ClN
3O
5Sn): theoretical value: C, 46.30, H, 5.30, N, 7.36; Measured value: C, 46.34, H, 5.35, N, 7.31.
IR(KBr,cm
-1):2971,2957ν(C-H),1617,1576ν(C=N),1528ν(C-NO
2),1356ν(C-N),1249ν(C-O),612ν(Sn-O),514ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):5.92(d,J=2.0Hz,1H,H-2),6.41(dd,J
1=2.0Hz,J
2=8.8Hz,1H,H-4),6.85(d,J=8.8Hz,1H,H-5),8.96(s,1H,H-7),8.55(d,J=2.0Hz,1H,H-9),7.97(dd,J
1=2.0Hz,J
2=9.2Hz,1H,H-11),7.48(d,J=9.2Hz,1H,H-12),3.45(q,J=6.8Hz,4H,-N(CH
2CH
3)
2),3.17(s,3H,CH
3OH),1.40-1.76(m,6H,H-α,H-β,H-γ),1.15(t,J=6.8Hz,6H,-N(CH
2CH
3)
2),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.42(CH
3OH),157.78(C-7),43.97(-N(CH
2CH
3)
2),12.58(-N(CH
2CH
3)
2),13.43(C-θ),25.25(C-α),26.97(C-γ),28.06(C-β),99.97,105.17,109.37,110.09,116.53,122.77,131.22,136.74,138.37,154.54,161.84,169.89(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3, D
c=1.494Mgm
-3, μ (MoK
α)=1.148mm
-1, F (000)=1160,2.30 °<θ<25.00 °, crystalline size: 0.31 * 0.29 * 0.27mm, R=0.0499, wR=0.1311.
Embodiment 17:
Monobutyltin 3, the preparation of 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5):
In round-bottomed flask, add successively in order 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali 0.193g (0.5mmol), monobutyl tin trichloride 0.141g (0.5mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5).Productive rate: 81%, fusing point: 165～166 ℃.
Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5) ultimate analysis (C
19H
22Br
2ClNO
3Sn): theoretical value: C, 36.43, H, 3.54, N, 2.24; Measured value: C, 36.40, H, 3.59, N, 2.21.
IR(KBr,cm
-1):2955,2925ν(C-H),1596,1576ν(C=N),1261ν(C-O),1000ν(C-Br),545ν(Sn-O),493ν(Sn-N),418ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.95(d,J=2.0Hz,1H,H-3),7.90(d,J=2.0Hz,1H,H-5),9.13(s,1H,H-7),7.59(s,1H,H-9),6.74(d,J=8.0Hz,1H,H-11),7.05(d,J=8.0Hz,1H,H-12),2.28(s,3H,Ar-CH
3),4.09(q,J=5.2Hz,1H,CH
3OH),3.17(d,J=5.2Hz,3H,CH
3OH),1.42-1.83(m,6H,H-α,H-β,H-γ),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),157.20(C-7),13.49(C-θ),25.20(C-α),26.77(C-γ),27.43(C-β),20.30(s,3H,Ar-CH
3),106.74,116.00,116.81,117.99,120.37,125.59,128.62,131.23,136.36,138.51,154.06,161.22(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3, D
c=1.871Mgm
-3, μ (MoK
α)=4.881mm
-1, F (000)=1216,1.56 °<θ<27.52 °, crystalline size: 0.10 * 0.09 * 0.08mm, R=0.0339, wR=0.0856.
Embodiment 18:
Monobutyltin 3, the preparation of 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5):
In round-bottomed flask, add successively 3 in order, 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali 0.770g (2.0mmol), monobutyl tin trichloride 0.587g (2.08mmol), sodium methylate 0.005g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5).Productive rate: 82%, fusing point: 165～166 ℃.
Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5) ultimate analysis (C
19H
22Br
2ClNO
3Sn): theoretical value: C, 36.43, H, 3.54, N, 2.24; Measured value: C, 36.40, H, 3.59, N, 2.21.
IR(KBr,cm
-1):2955,2925ν(C-H),1596,1576ν(C=N),1261ν(C-O),1000ν(C-Br),545ν(Sn-O),493ν(Sn-N),418ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.95(d,J=2.0Hz,1H,H-3),7.90(d,J=2.0Hz,1H,H-5),9.13(s,1H,H-7),7.59(s,1H,H-9),6.74(d,J=8.0Hz,1H,H-11),7.05(d,J=8.0Hz,1H,H-12),2.28(s,3H,Ar-CH
3),4.09(q,J=5.2Hz,1H,CH
3OH),3.17(d,J=5.2Hz,3H,CH
3OH),1.42-1.83(m,6H,H-α,H-β,H-γ),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),157.20(C-7),13.49(C-θ),25.20(C-α),26.77(C-γ),27.43(C-β),20.30(s,3H,Ar-CH
3),106.74,116.00,116.81,117.99,120.37,125.59,128.62,131.23,136.36,138.51,154.06,161.22(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3, D
c=1.871Mgm
-3, μ (MoK
α)=4.881mm
-1, F (000)=1216,1.56 °<θ<27.52 °, crystalline size: 0.10 * 0.09 * 0.08mm, R=0.0339, wR=0.0856.
Embodiment 19:
Monobutyltin 3, the preparation of 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5):
In round-bottomed flask, add successively 3 in order, 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali 0.385g (1.0mmol), monobutyl tin trichloride 0.288g (1.02mmol), sodium methylate 0.0005g (0.01mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5).Productive rate: 75%, fusing point: 165～166 ℃.
Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5) ultimate analysis (C
19H
22Br
2ClNO
3Sn): theoretical value: C, 36.43, H, 3.54, N, 2.24; Measured value: C, 36.40, H, 3.59, N, 2.21.
IR(KBr,cm
-1):2955,2925ν(C-H),1596,1576ν(C=N),1261ν(C-O),1000ν(C-Br),545ν(Sn-O),493ν(Sn-N),418ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.95(d,J=2.0Hz,1H,H-3),7.90(d,J=2.0Hz,1H,H-5),9.13(s,1H,H-7),7.59(s,1H,H-9),6.74(d,J=8.0Hz,1H,H-11),7.05(d,J=8.0Hz,1H,H-12),2.28(s,3H,Ar-CH
3),4.09(q,J=5.2Hz,1H,CH
3OH),3.17(d,J=5.2Hz,3H,CH
3OH),1.42-1.83(m,6H,H-α,H-β,H-γ),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),157.20(C-7),13.49(C-θ),25.20(C-α),26.77(C-γ),27.43(C-β),20.30(s,3H,Ar-CH
3),106.74,116.00,116.81,117.99,120.37,125.59,128.62,131.23,136.36,138.51,154.06,161.22(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3, D
c=1.871Mgm
-3, μ (MoK
α)=4.881mm
-1, F (000)=1216,1.56 °<θ<27.52 °, crystalline size: 0.10 * 0.09 * 0.08mm, R=0.0339, wR=0.0856.
Embodiment 20:
Monobutyltin 3, the preparation of 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5):
In round-bottomed flask, add successively 3 in order, 5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali 0.578g (1.5mmol), monobutyl tin trichloride 0.444g (1.575mmol), sodium methylate 0.0016g (0.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5).Productive rate: 79%, fusing point: 165～166 ℃.
Monobutyltin 3,5-Dibromosalicylaldehyde contracting 4-methyl o-aminophenol Schiff alkali title complex (I-5) ultimate analysis (C
19H
22Br
2ClNO
3Sn): theoretical value: C, 36.43, H, 3.54, N, 2.24; Measured value: C, 36.40, H, 3.59, N, 2.21.
IR(KBr,cm
-1):2955,2925ν(C-H),1596,1576ν(C=N),1261ν(C-O),1000ν(C-Br),545ν(Sn-O),493ν(Sn-N),418ν(Sn-C).
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.95(d,J=2.0Hz,1H,H-3),7.90(d,J=2.0Hz,1H,H-5),9.13(s,1H,H-7),7.59(s,1H,H-9),6.74(d,J=8.0Hz,1H,H-11),7.05(d,J=8.0Hz,1H,H-12),2.28(s,3H,Ar-CH
3),4.09(q,J=5.2Hz,1H,CH
3OH),3.17(d,J=5.2Hz,3H,CH
3OH),1.42-1.83(m,6H,H-α,H-β,H-γ),0.93(t,J=7.2Hz,3H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):48.41(CH
3OH),157.20(C-7),13.49(C-θ),25.20(C-α),26.77(C-γ),27.43(C-β),20.30(s,3H,Ar-CH
3),106.74,116.00,116.81,117.99,120.37,125.59,128.62,131.23,136.36,138.51,154.06,161.22(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3, D
c=1.871Mgm
-3, μ (MoK
α)=4.881mm
-1, F (000)=1216,1.56 °<θ<27.52 °, crystalline size: 0.10 * 0.09 * 0.08mm, R=0.0339, wR=0.0856.
Test example: Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex of the present invention (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) or title complex (I-5), its Anticancer Activity in vitro is measured and is realized by the MTT experimental technique.
The MTT analytical method:
With viable cell metabolite reductive agent 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide be the basis.Succinodehydrogenase in the viable cell plastosome can make exogenous MTT be reduced to water-insoluble bluish voilet crystallization first a ceremonial jade-ladle, used in libation (Formazan) and be deposited in cell, and dead cell is without this function.First a ceremonial jade-ladle, used in libation in dimethyl sulfoxide (DMSO) (DMSO) energy dissolved cell, the optical density(OD) with microplate reader mensuration characteristic wavelength, can reflect viable cell quantity indirectly.
Adopt mtt assay to measure Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) or title complex (I-5) the inhibition activity to human cervical carcinoma cell (Hela), human breast cancer cell (MCF7), human liver cancer cell (HepG2), human colon cancer cell (Colo205), human lung carcinoma cell (NCI-H460).
Cell strain and culture system: Hela, MCF7, HepG2, Colo205 and NCI-H460 cell strain are taken from U.S.'s tissue culture storehouse (ATCC).With the RPMI1640 that contains 10% foetal calf serum (GIBICO company) substratum, at 5% (volume fraction) CO
2, carry out vitro culture in 37 ℃ of saturated humidity incubators.
Test process: will test liquid (0.1nM-10uM) and join respectively in each hole according to the concentration gradient of concentration, each concentration is established 6 parallel holes.Experiment is divided into drug test group (the test medicine that adds respectively different concns), control group (only add nutrient solution and cell, do not add the test medicine) and blank group (only add nutrient solution, do not add cell and test medicine).Orifice plate after dosing is placed in to 37 ℃, 5%CO
2In incubator, cultivate 72h.The activity of control drug is measured according to the method for specimen.In having cultivated the orifice plate after 72h, every hole adds MTT40uL (being made into 4mg/mL with the D-Hanks damping fluid).After 37 ℃ of placement 4h, remove supernatant liquor.Every hole adds 150uLDMSO, and vibration 5min, make the Formazan dissolving crystallized.Finally, utilize automatic microplate reader at 570nm wavelength place, to detect the optical density(OD) in each hole.
Data processing: data processing is used Graph Pad Prism version5.0 program, title complex IC
50By the nonlinear regression model (NLRM) that has S shape dose response in program, carrying out match obtains.
With the MTT analytical method, human cervical carcinoma cell (Hela) cell strain, human breast cancer cell (MCF7) cell strain, human liver cancer cell (HepG2) cell strain, human colon cancer cell (Colo205) cell strain, human lung carcinoma cell (NCI-H460) cell strain are analyzed, measured its IC
50Value, result is as shown in table 1, conclusion is: as can be known by data in table, with Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex of the present invention (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) or title complex (I-5) as cancer therapy drug, higher to human cervical carcinoma, human breast carcinoma, people's liver cancer, human colon carcinoma, people's lung cancer activity, can be used as the candidate compound of cancer therapy drug.
Table 1 Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) or title complex (I-5) cancer therapy drug external activity test data
Claims (19)
1. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex, is characterized in that, is the title complex of following structural formula (I):
Wherein Bu represents normal-butyl, R
1For-H ,-Cl or-Br, R
2For-H or-N (CH
2CH
3)
2, R
3For-H ,-Cl or-Br, R
4For-H ,-Cl ,-NO
2Or-Me.
2. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R
1For-Cl, R
2For-H, R
3For-Cl, R
4During for-Cl, structural formula (I) is in title complex (I-1).
3. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 2, is characterized in that, described title complex (I-1) is crystalline structure.
4. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 3, it is characterized in that, the crystallographic data of described title complex (I-1): oblique system, spacer C2/c, a=2.34004 (4) nm, b=0.96340 (2) nm, c=1.96692 (3) nm, α=γ=90 °, β=98.0530 (10) °, Z=8, V=4.39049 (14) nm
3In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
5. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R
1For-H, R
2For-H, R
3For-Br, R
4For-NO
2The time, structural formula (I) is in title complex (I-2).
6. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 5, is characterized in that, described title complex (I-2) is crystalline structure.
7. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 7, is characterized in that the crystallographic data of described title complex (I-2): triclinic(crystalline)system, spacer
A=0.88989 (2) nm, b=1.14166 (3) nm, c=1.20767 (3) nm, α=86.0090 (10) °, β=86.6620 (10) °, γ=71.5650 (10) °, Z=2, V=1.16030 (5) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
8. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R
1For-Cl, R
2For-H, R
3For-Cl, R
4During for-H, structural formula (I) is in title complex (I-3).
9. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 8, is characterized in that, described title complex (I-3) is crystalline structure.
10. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 9, it is characterized in that, the crystallographic data of described title complex (I-3): oblique system, spacer C2/c, a=2.62445 (13) nm, b=0.95746 (5) nm, c=1.94558 (10) nm, α=γ=90 °, β=120.0070 (10) °, Z=8, V=4.2336 (4) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
11. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R
1For-H, R
2For-N (CH
2CH
3)
2, R
3For-H, R
4For-NO
2The time, structural formula (I) is in title complex (I-4).
12. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 11 is characterized in that described title complex (I-4) is crystalline structure.
13. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 12, is characterized in that the crystallographic data of described title complex (I-4): oblique system, spacer P2
1/ n, a=1.65034 (17) nm, b=0.99397 (10) nm, c=1.73485 (18) nm, α=γ=90 °, β=116.932 (2) °, Z=4, V=2.5372 (5) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
14. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R
1For-Br, R
2For-H, R
3For-Br, R
4During for-Me, structural formula (I) is in title complex (I-5).
15. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 14 is characterized in that described title complex (I-5) is crystalline structure.
16. Monobutyltin substituted salicylic aldehydes contracting arylamine Schiff alkali title complex as claimed in claim 14, is characterized in that the crystallographic data of described title complex (I-5): oblique system, spacer P2
1/ c, a=1.3431 (2) nm, b=1.7458 (3) nm, c=0.97546 (17) nm, α=γ=90 °, β=103.494 (3) °, Z=4, V=2.2240 (7) nm
3.In molecule, tin atom and ligating atom form hexa-coordinate distorted octahedron configuration.
17. the preparation method of the described Monobutyltin substituted salicylic aldehydes of claim 1 to 16 any one claim contracting arylamine Schiff alkali title complex, it is characterized in that adding successively in order substituted salicylic aldehydes contracting arylamine Schiff alkali, monobutyl tin trichloride, sodium methylate and solvent anhydrous methanol in reaction vessel, under stirring and refluxing, react 8～12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain crystal, be Monobutyltin 3,5-dichloro-salicylaldehyde contracting 4-chlorine o-aminophenol Schiff alkali title complex;
Wherein substituted salicylic aldehydes contracting arylamine Schiff alkali, monobutyl tin trichloride are reactant, sodium methylate is catalyzer, anhydrous methanol is reaction solvent, reactant substituted salicylic aldehydes contracting arylamine Schiff alkali is 1:1～1:1.05 with the amount of substance ratio of monobutyl tin trichloride, the catalyzer sodium methylate is 0.004:1～0.05:1 with the amount of substance ratio of reactant substituted salicylic aldehydes contracting arylamine Schiff alkali, and the consumption of solvent anhydrous methanol is that every mmole monobutyl tin trichloride adds 30～55 ml methanol.
18. the application of the described Monobutyltin substituted salicylic aldehydes of claim 1 to 16 any one claim contracting arylamine Schiff alkali title complex in preparing the medicine for treating tumor thing.
19. the described application of claim 18, its described tumour are cervical cancer, anti-breast cancer, anti-liver cancer, inhibitor against colon carcinoma cells or anti-lung cancer.
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| CN105348328A (en) * | 2015-10-10 | 2016-02-24 | 衡阳师范学院 | 3, 5-dichloro salicylaldehyde 4-nitro-o-aminophenol condensate Schiff base and pyridine-containing nickel complex and preparation method and application |
| CN105777795A (en) * | 2016-04-11 | 2016-07-20 | 衡阳师范学院 | 5-chlorosalicylaldehyde contraction 4-nitro-o-aminophenol Schiff alkali diphenyl tin complex and preparing method and application thereof |
| CN105777796A (en) * | 2016-04-11 | 2016-07-20 | 衡阳师范学院 | 3,5-dibromosalicylaldehyde contraction 4-nitro-o-aminophenol Schiff alkali diphenyl tin complex and preparing method and application thereof |
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