6-methylquinoline is mainly used in organic synthesis, such as the prep work of 6-aminomethylquinoline. The artificial technique reported in the literary works is to make use of 6-quinoline formic acid as resources to acquire 6-quinoline carboxamide through amination reaction, and afterwards Dehydration response gets 6-cyanoquinoline, and ultimately obtains 6-aminomethylquinoline under Raney nickel reduction, and the complete yield of this reaction gets to 44.4%, but there are many action in this response, and also the N used in the amination response, N-carbonyldiimidazole is costly, as well as Raney nickel is made use of in 6-cyanoquinoline, which requires high response as well as troublesome procedure. As a result, it is of excellent relevance to find as well as optimize the preparation route of 6-aminomethylquinoline.
There are research studies, using 6-methylquinoline, bromosuccinimide, potassium phthalimide, as well as hydrazine moisturize as basic materials to obtain 6-aminomethylquinoline through bromination and Gabriel response, and also the synthesis steps of the technique less, the response conditions are moderate, the Gabriel reaction with hydrazine hydrate has a greater yield than the acid-base decrease, and the side responses are fairly much less, which provides a brand-new reference technique for the prep work of 6-aminomethylquinoline.
The specific approach is as adheres to:
1) Synthesis of 6-bromomethylquinoline: In a three-necked flask geared up with a reflux condenser as well as a drying out tube, add 240 mL of carbon tetrachloride, slowly warm to 50 ° C, and after that include 6-methylquinoline (5.72 g, 0.04 mol), N-bromosuccinimide (7.12 g, 0.04 mol), azobisisobutyronitrile (0.656 g, 0.004 mol), mixed and refluxed at 80 ° C for 12 h, TLC detected completion of the reaction (The eluent is ethyl acetate-petroleum ether-triethylamine, the quantity proportion is 3:1:0.1), cooled down to room temperature level, filteringed system, the filtrate was cleaned 3 times with saturated NaCl service, the mixed organic layers were dried over anhydrous Na2SO4, filteringed system, and also recovered carbon tetrachloride under minimized stress to obtain 7.876 g of a yellow solid with a return of 88.7% and also a melting point of 73-75 ° C.
2) Synthesis of quinoline 6-methylphthalimide: Add 6-bromomethylquinoline (6.7 g, 0.03 mol), o- Phthalimide potassium salt (4.5 g, 0.03 mol), N,N-dimethylformamide 50 mL, gradually heat up to 60 ° C, respond for 3 h, stir at room temperature level for 12 h, as well as find completion factor of the response by thin-layer chromatography (The eluent is ethyl acetate-petroleum ether-triethylamine, quantity proportion 3:1:0.1), include 40 mL of chloroform, 120 mL of water, mix well, filter, different the natural layer, and also clean the water layer with trichloromethane Wash with methane (10 mL × 2), integrate the organic layers, laundry with 0.2 mol/L NaOH option, clean with water successively, completely dry with anhydrous Na2SO4, filter, recuperate chloroform under minimized pressure, include 25 mL of anhydrous ether, stir well, It was filteringed system and also dried in vacuo to obtain 3.5 g of strong with a return of 40.0% as well as a melting point of 163-165 ° C.
3) Synthesis of 6-aminomethylquinoline: In a three-necked flask with a reflux condenser, add quinoline 6-methylphthalimide (2.88 g, 0.01 mol) as well as 80% hydrazine hydrate (1.3 mL, 0.02 mol) and also 50 mL of methanol, stirred and refluxed at 70 ° C for 4 h, as well as the end factor of the reaction was detected by thin-layer chromatography (the eluent was ethyl acetate-petroleum ether-triethylamine, the quantity ratio was 3:1: 0.1), trendy, include 20 mL of water, recover methanol under decreased pressure, include 25 mL of focused HCl, reflux at 80-90 ° C for 1 h, amazing to 0 ° C, filter, recuperate focused HCl under lowered stress, include 50 mL of water, filter, as well as make use of the filtrate Readjust the pH to 8-9 with 2 mol/L NaOH, cool at 0 ° C for 12 h, filter, as well as dry in vacuo to get 1.569 g of solid with a yield of 98.7% as well as a melting point of 165-167 ° C.
On top of that, 6-methylquinoline can also be utilized to prepare insect repellents. Over the last few years, study has been conducted on methods for fending off bugs by using adjustments to the chemosensory system possessed by the insects to deteriorate the cognitive sensations of the bugs. And use N,N-diethyl-3-methylbenzamide (DEET) or p-menthane-3,8-diol (PMD) as well as various other materials that act on olfactory receptors as repellents. Nonetheless, DEET has an undesirable smell as well as high skin penetration, so there is a problem that use to babies or individuals with sensitive skin is restricted, and also the period is just 2 to 3 hrs.
Some research studies have established an insect repellent, in which, octahydro-7-methyl-1,4-methylenenaphthalene-6(2H)-one, 3-methyl-5-propyl-2 -cyclohexene-1-one, octahydro-5-methoxy-4,7-methylene-1H-indene-2-carboxaldehyde, 6-methylquinoline, phenoxyacetaldehyde, γ- Caprylactone, 9-ethylidene-3-oxatricyclo(6.2.1.02,7)undecane-4-one, 2,3,3-trimethyl-2H-inden-1-one, 4 -Methyl-5-thiazole ethanol, 7-methoxy-3,7-dimethyloctanal, 3-methyl-1-phenyl-3-pentanol, 2-phenylpropanal dimethyl acetal One or more compounds selected from aldehyde, octahydro-2H-1-chromen-2-one as well as 2,6,6-trimethylcyclohexa-1,3-diene-1-carbonaldehyde as Energetic ingredients.
Those bug spray or thermosensing inhibitor can be applied to the skin of mammals including human beings, attached to or kept in straight or indirect contact with the skin, such as garments, accessories, etc, or sprayed inside your home, It can be utilized to ward off bugs in a fixed space such as an automobile (including dissipation or volatilization), and also can be prepared in the form of a make-up by properly mixing other ingredients such as solvents or different formula additives according to the usage technique. Those bug spray or thermosensitivity inhibitor can additionally be made use of as a material for imparting insect repellent activity to skin exterior preparations, cleansers, skin cosmetics, hair cosmetics, fabric softeners, fabric therapy agents, and so forth.
