CN108558789B - A kind of preparation and synthetic method of thiazoline hydrochloride - Google Patents

A kind of preparation and synthetic method of thiazoline hydrochloride Download PDF

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Publication number
CN108558789B
CN108558789B CN201810311808.XA CN201810311808A CN108558789B CN 108558789 B CN108558789 B CN 108558789B CN 201810311808 A CN201810311808 A CN 201810311808A CN 108558789 B CN108558789 B CN 108558789B
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Prior art keywords
amino
methylbenzothiazole
crystal
benzaldehyde
slowly added
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CN108558789A (en
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罗梅
丁超
卞杰
郭晨晨
张竟成
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of 2- amino -4- methylbenzothiazole hydrochloride, chemical formula are as follows:(I) synthetic method of compound I, it is to weigh 0.3292g 2- amino -4- methylbenzothiazole in 100mL beaker, 20mL anhydrous methanol is added, constantly stir, after solid medicine dissolution, about 1.5mL concentrated hydrochloric acid is slowly added dropwise, is stirring evenly and then adding into 0.2379g cobalt chloride hexahydrate, is slowly added into 10mL anhydrous ether after its dissolution (above-mentioned whole process is kept stirring).It is then allowed to stand, the colorless and transparent crystal after about four days.Crystal is filtered out, is washed with acidic methanol solution, is dried in vacuo 30 minutes, obtains colorless and transparent rhomboidan；The purposes of compound I, benzaldehyde Henle reaction and benzaldehyde and show preferable catalytic performance, conversion ratio is respectively up to 53% and 88%.

Description

A kind of preparation and synthetic method of thiazoline hydrochloride
One, technical field
The present invention relates to a kind of preparation of quaternary ammonium salt and synthetic methods, are exactly a kind of synthesis of thiazoline hydrochloride Method.
Two, background technique
There are many document reports for the synthetic method of quaternary ammonium salt.Early in 1956, Japanization association reported some quaternary ammoniums The synthetic method of salt, nineteen fifty-nine, American Chemical Society also report the synthetic method of quaternary ammonium salt.
Bibliography:
1.Surrey,Alexander R.；Lesher,George Y.；Mayer,J.Richard；Webb, Wm.G.Journal of the American Chemical Society(1959),81 2894-7；
2.Davis,M.Journal of the Chemical Society(1956),337-43。
Applicant does not obtain target product complex in the experiment of synthetic compound, has but obtained another newcooperative medical system Close object thiazoline hydrochloride.
Three, summary of the invention
The present invention is intended to provide thiazoline hydrochloride, the technical problem to be solved is that one-step synthesis to obtain target product.
A kind of so-called thiazoline hydrochloride of the present invention is by 2- amino -4- methylbenzothiazole and cobalt chloride hexahydrate system It is standby by following below formula compound represented:
Chemical name: 2- amino -4- methylbenzothiazole hydrochloride, abbreviation compound (I).
This synthetic method includes synthesis and separation, and the synthesis is to weigh 0.3292g 2- amino -4- methyl benzo thiophene Azoles is added 20mL anhydrous methanol, constantly stirs in 100mL beaker, and after solid medicine dissolution, about 1.5mL is slowly added dropwise Concentrated hydrochloric acid is stirring evenly and then adding into 0.2379g cobalt chloride hexahydrate, and it is (above-mentioned to be slowly added into 10mL anhydrous ether after its dissolution Whole process is kept stirring).It is then allowed to stand, the colorless and transparent crystal after about four days.Crystal is filtered out, acidic methanol is used Solution washing, colorless and transparent rhomboidan after vacuum drying 30 minutes.
Compound I divides in the Henle reaction and benzaldehyde of benzaldehyde with preferable catalytic performance, conversion ratio is shown Not up to 53% and 88%.
One step of this synthetic method obtains target product, and simple process is easy to operate.
The reaction mechanism of the reaction is that 2- amino -4- methylbenzothiazole is reacted with cobalt chloride hexahydrate, in acid condition Under, 2- amino -4- methylbenzothiazole and hydrochloric acid act on, and form 2- amino -4- methylbenzothiazole hydrochloride.
Four, Detailed description of the invention
Fig. 1 is the X- diffraction analysis figure of 2- amino -4- methylbenzothiazole quinoline hydrochloride.
Five, specific embodiment
1. the preparation of a hydration 2- amino -4- methylbenzothiazole quinoline hydrochloride
0.3292g 2- amino -4- methylbenzothiazole is weighed in 100mL beaker, 20mL anhydrous methanol is added, constantly Ground stirring is slowly added dropwise about 1.5mL concentrated hydrochloric acid, is stirring evenly and then adding into six chloride hydrate of 0.2379g after solid medicine dissolution Cobalt is slowly added into 10mL anhydrous ether after its dissolution (above-mentioned whole process is kept stirring).It is then allowed to stand, the nothing after about four days The transparent crystal of color.Crystal is filtered out, is washed with acidic methanol solution, is dried in vacuo 30 minutes.Final products are colourless Transparent rhomboidan surveys its fusing point with thermal station micro-meldometer, and observation discovery crystal starts to lose translucency at 112 DEG C, White-opalescent solid is gradually become, starts to distil at 200 DEG C or so, at 224 DEG C or so, sample almost all distils, during which Do not observe that sample has apparent melting phenomenon；Elemental analysis data: C8H11ClN2OS, theoretical value: C:43.94%, H: 5.07%, N:12.81%；Measured value: C:44.14%, H:5.16%, N:12.80%；The error of measured value and theoretical value difference Are as follows: C:0.55%, H:2.58%, N:12.80%；Ir data (KBr；γ；cm-1): 3430,3238,3081,2724, 1649,1588,1483,1247,872,775,610,479；
Compound crystal data are as follows:
Empirical formula C8H11Cl N2OS
Molecular weight 218.70
Temperature 296 (2) K
Wavelength
Crystallographic system, space group anorthic system, P bca
Cell parameterα=90 °
β=90 °
γ=90 °
Volume
Charge density 8,1.431Mg/m^3
Absorption correction parameter 0.544mm^-1
Number of electrons 912 in unit cell
Crystal size 0.200x 0.170x 0.130mm
The range 2.897to 25.997 at the angle Theta
Index capture range -12≤h≤12 of HKL, -16≤k≤16, -19≤l≤19
Collection/independent diffraction data 26246/1987 [R (int)=0.0653]
Theta=25.242 ° of data integrity degree 99.6%
The method Multi Slice Mode of absorption correction
The transmitance 0.7456and 0.6060 of minimax
The Matrix least square method for the method F^2 that refine uses
Data number/use limitation number/number of parameters 1987/4/140
The method 1.127 that refine uses
Consistency factor R 1=0.0403, the ω R2=0.1060 of point diffraction
The identical factor R 1=0.0443, ω R2=0.1090 of observable diffraction
Absolute configuration parameter 0.0037 (13)
Maximum summit and peak valley 0.394and-0.241e.A^-3 on difference Fourier figure
The typical bond distance's data of crystal:
The typical bond angle data of crystal:
2. Henle reaction application
0.0328g (0.15mmol) crystal is weighed in 25mL round-bottomed flask, 2mL anhydrous methanol, 0.1mL benzene first is added Aldehyde, 0.5mL nitromethane after being stirred to react 48 hours under room temperature, carry out1HNMR detection, conversion ratio 53%；1H NMR (300MHz,CDCl3) 7.28~7.32 (m, 5H, Ar-H), 5.32~5.35 (d, J=9.18Hz, 1H ,-CH), 4.38~4.56 (m,2H,-CH2),3.89(br,1H,-OH)。
3. benzaldehyde is reacted with benzamide
Benzaldehyde is also a kind of common organic synthesis with reacting for benzamide, is that one kind of synthesizing amide is important Method.It is also widely used in terms of organic medicinal intermediate.
The reaction equation of experiment:
In 25mL two-mouth bottle, be added 0.0659g complex I, 2mLTHF and chlorobenzene 2mL, 0.05mL benzaldehyde and 0.1302g benzamide has crystal appearance after back flow reaction 24 hours；It carries out1HNMR detection；Catalytic conversion is 88%；1HNMR(500MHz,CDCl3, 27 DEG C), δ (ppm)=9.02 (d, J=7.77Hz, 2H), 7.91 (d, J=7.42Hz, 4H), 7.54 (t, J=7.4Hz, 2H), 7.47 (t, J=7.7Hz, 6H), 7.37 (t, J=7.7Hz, 2H), 7.30 (t, J=7.3Hz, 1H), 7.03 (t, J=7.9Hz, 1H).

Claims (4)

1. a kind of 2- amino -4- methylbenzothiazole hydrochloride, chemical formula are as follows:
2. 2- amino -4- methylbenzothiazole hydrochloride described in claim 1, at a temperature of 296K, in Oxford X-ray list On brilliant diffractometer, with the MoK alpha ray through graphite monochromator monochromatization,Diffraction number is collected with ω-θ scanning mode According to, it is characterised in that crystal category orthorhombic system, space group anorthic system, Pbca；Cell parameter:α=90 °；β=90 °；γ=90 °.
3. the synthetic method of 2- amino -4- methylbenzothiazole hydrochloride described in claim 1, is to weigh 0.3292g2- ammonia Base -4- methylbenzothiazole is added 20mL anhydrous methanol, constantly stirs in 100mL beaker, after solid medicine dissolution, About 1.5mL concentrated hydrochloric acid is slowly added dropwise, is stirring evenly and then adding into 0.2379g cobalt chloride hexahydrate, is slowly added into after its dissolution 10mL anhydrous ether, is then allowed to stand, the colorless and transparent crystal after about four days.Crystal is filtered out, with acidic methanol solution Washing is dried in vacuo 30 minutes, obtains colorless and transparent rhomboidan.
4. the purposes of 2- amino -4- methylbenzothiazole hydrochloride described in claim 1, henry of the compound I in benzaldehyde Show preferable catalytic performance in the reacting of benefit reaction and benzaldehyde and benzamide, conversion ratio respectively up to 53% and 88%.
CN201810311808.XA 2018-04-09 2018-04-09 A kind of preparation and synthetic method of thiazoline hydrochloride Expired - Fee Related CN108558789B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898342A (en) * 2012-10-28 2013-01-30 罗梅 Chiral compound
CN103012447A (en) * 2013-01-20 2013-04-03 罗梅 Chiral oxazoline zinc complex

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898342A (en) * 2012-10-28 2013-01-30 罗梅 Chiral compound
CN103012447A (en) * 2013-01-20 2013-04-03 罗梅 Chiral oxazoline zinc complex

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