2. Ethanol method: using ethanol and sodium hydroxide instead of sodium ethoxide, using solid-liquid phase transfer catalysis method and PTC as catalyst.
3. Benzoyl chloride method: Benzoyl chloride, formamide and anhydrous ethanol are used as raw materials to generate a mixture of triethyl orthoformate, benzoic acid and ammonium chloride under the action of a catalyst, and the finished products triethyl orthoformate and benzoic acid are obtained after separation.
4. Put 3 liters of absolute ethanol and 490 grams (327 ml, 4. 1 mol) of chloroform into a 5-liter round-bottomed flask with a reflux condenser, which should be placed in a place where it can be easily cooled by running water. 207 g (9 g atom) of clean sodium metal was cut into small pieces so that it could fall from the condenser and then added to the solution in about two hours. In order to add metallic sodium at this rate, the flask must be cooled when adding sodium. When the metallic sodium completely reacts and the mixture is cooled to room temperature, sodium chloride is filtered by suction filtration with a drying instrument, and the sodium oxide on the filter paper is washed with 200ml absolute ethanol, so that the washing liquid flows into the filtrate obtained above. Put the filtrate into a 3-liter flask equipped with an 80 cm fractionator, and evaporate excess chloroform and most ethanol in a steam bath or water bath. The distillate was collected in a 2-liter suction filter bottle with a drying tank to isolate moisture. Distillation takes 5 to 6 hours. The mixture of chloroform and ethanol recovered from the distillation towel weighs about 2000 grams and can be used in the next experiment. The remaining liquid in the flask was decanted to remove a small amount of sodium halide, poured into a Kjeldahl flask with a 30 cm radium column, and distilled at atmospheric pressure. The fraction below 85℃ is mainly ethanol, and * * * is discarded; The fraction at 85- 140℃ is about 100g, accounting for about a quarter of the total yield of ethyl orthoformate. This part can be carried out in stages, but it is best to combine it with the products of the next experiment. The crude methyl enemy vinegar was distilled at lbj 140- 146℃, and the weight was120 ~140g (27-31%). After the first experiment, 400 grams of chloroform phase (800- 1000 ml) was added to the recovered chloroform-ethanol mixture to make the total amount reach 3 liters. Then add metal sodium with the front rod. Excess chloroform and ethanol were distilled from the distillation column, added to the middle part of the final experiment, and then fractionated. The yield of this experiment is about 200g and 45%.
Quality standard:
The content is 99.0%
Moisture ≤0.07%
Chromaticity ≤20# (APHA)
Uses: pharmaceutical raw materials, photographic drugs, photosensitive materials, anti-blooming dyes, cyanine dyes and synthetic pesticides.
It is used as an intermediate in the production of medicines and pesticides such as pipemidic acid, diethyl ethoxymethylene malonate (EMME), Allen, amitraz, ciprofloxacin and levofloxacin. And the synthesis of antimalarial drugs chloroquine and quinpiprazole, methylene dyes, cyanine dyes, developing sensitizers, acrylic fibers and other products.
1. triethyl orthoformate is a commonly used alkylation reagent and formylation reagent in chemical laboratories. They are easy to store, but highly reactive.
They can be used as alkylating agents and can easily transfer alkyl groups to hydroxyl groups of various alcohols; When used as a formylation reagent, it can be used under acidic and alkaline conditions.
When triethyl orthoformate is used as alkylation reagent, various alcohols can undergo corresponding alkylation reaction. Alkylation of polyols can generate corresponding cyclic orthoformate aldehydes or ketones, and orthoformate can be used to protect aldehydes and ketones. Orthoformate can be used as formylation reagent under the catalysis of Lewis acid. Compared with other formylation reagents, orthoformate has the characteristics of simple operation and high yield. Under the catalysis of acid, orthoformate can easily generate dialkoxy carbonium ion in situ, which can be directly used in formylation reaction. The formylation reaction can react with enol (or analogue) on the ortho-α-C of carbonyl group, and the silyl ether of enol or enol salt of ketone can react with carbonium ion generated in situ by orthoformate to generate β -aldosterone compound.
2. Used in organic synthesis, pharmaceutical intermediates and photosensitive materials.
Storage method: storage precautions [27] Store in a cool and ventilated warehouse. Stay away from fire and heat sources. The reservoir temperature should not exceed 37℃. Keep the container sealed. Should be stored separately from oxidants, acids, etc. , and should not be mixed. Adopt explosion-proof lighting and ventilation facilities. It is forbidden to use mechanical equipment and tools that are easy to generate sparks. The storage area should be equipped with emergency response equipment for leakage and suitable accommodation materials.
References:
Reaction of 1 2,2-pentadiene13- dioxane-4,6-dione with triethyl orthoformate and aromatic amine: Ding Weiwei; Water Lin Bao Organic Chemistry 199 1 (3), 3 18-32 1
Yan Guohe, A New Method for Preparing Triethyl Orthoformate: Hu Zhongkan China Journal of Medicine1991(11), 5 12-5 12.
Application of gas chromatography analysis in triethyl orthoformate production; Han Kezhong Gansu Chemical Industry 1992 (2), 25-28
Synthesis of triethyl orthoformate by solid-liquid phase transfer catalysis: Xue; Gu Zhiqiang's chemical reagent 1992 (5), 317,305.
5 Cui Xueyuan, a new synthetic process of triethyl orthoformate; Jin Jiangsu Chemical Industry1996 (5) 26-27,43
Synthesis of triethyl orthoformate by six-phase transfer catalysis: China Journal of Medicine 1996 (1), 36-37.
7 production method of triethyl orthoformate Zhu Bingqian; Hebei Lili Chemical Industry 1997 (3), 24-25
Gas chromatographic analysis of triethyl orthoformate: Boyaluo pesticide 1997 (2), 20-2 1.
9 New Synthesis Process of Triethyl Orthoformate Yang Shengqiang Guangxi Chemical Industry 1998 (1), 60-6 1
Determination of triethyl orthoformate 2002 (4); Reference 4
Synthesis of 1- substituted-1, 2,4-triazole -5- one by triethyl orthoformate Zhang Juan: Fan Xiaodong; Liu Yifeng; Journal of Li Hua Northwest University. Natural Science Edition 2006 (3), 4 10-4 12.