CN103319302B - Preparation method of heptachloropropane - Google Patents
Preparation method of heptachloropropane Download PDFInfo
- Publication number
- CN103319302B CN103319302B CN201310270566.1A CN201310270566A CN103319302B CN 103319302 B CN103319302 B CN 103319302B CN 201310270566 A CN201310270566 A CN 201310270566A CN 103319302 B CN103319302 B CN 103319302B
- Authority
- CN
- China
- Prior art keywords
- reaction
- tetracol phenixin
- temperature
- trieline
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a preparation method of heptachloropropane. The heptachloropropane is prepared from trichloro ethylene and carbon tetrachloride through electrophilic addition reaction in the presence of lewis acid serving as a catalyst, wherein the lewis acid can be aluminum trichloride, zinc chloride or stannic chloride. The preparation method disclosed by the invention adopts the lewis acid as a catalyst, is high in catalysis efficiency, convenient and safe to operate, environment-friendly, simple in equipment, and suitable for continuous and mass production, reduces reaction time, and improves yield.
Description
Technical field
The present invention relates to a kind of preparation method of heptachloropropane.
Background technology
Tradition powder extinguishing agent primarily of activity put out a fire component, hydrophobic ingredient, inert filler composition.Hydrophobic ingredient mainly contains silicone oil and hydrophobic silicic aerogels; Inert filler is of a great variety, main plays anti-jolt ramming, caking, improves dry powder exercise performance, catalysis dry powder silicone oil polymerization and to improve and fire foam common such as to hold at the effect.This kind of traditional powder extinguishing agent has at home and abroad obtained at present and has very generally applied.
Tradition halon extinguishing agent, the halogen ion in molecule contributes to thermostability and the unreactiveness of fire-fighting medium, is the effective constituent of fire-fighting medium in fire extinguishing procedure.The fire-fighting principle of this kind of fire-fighting medium, mainly halogen ion damaged fuel produces hydrionic chain chemical reaction in combustion, and interruption is burnt and reaches the object of fire extinguishing.Be applicable to put out a fire to save life and property various inflammable, combustible liquid fire and electrical equipment fire.
At present, 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane is the analogue of powder type fire extinguisher main raw, and be difficult to burning, density is greater than water, should be solid-state, can slowly decompose in atmosphere under normal temperature, does not stay residue, has good gas phase electrical insulating property after vaporization.Traditional method adopts trieline and carbon tetrachloride reaction to prepare heptachloropropane, long reaction time, and productive rate is low, therefore needs to seek a kind of effective catalyzer and improves reaction efficiency.
Summary of the invention
The object of the invention is, in order to solve the defect existed in prior art, to provide the heptachloropropane preparation method that a kind of reaction efficiency is high.
In order to achieve the above object, the invention provides a kind of preparation method of heptachloropropane, adopt trieline and tetracol phenixin to be raw material, be catalyzer with Lewis acid, prepared by electrophilic addition reaction; Lewis acid is selected from aluminum chloride, zinc chloride or tin tetrachloride.
Wherein, trieline, tetracol phenixin, lewis acidic add-on are 30mL:35 ~ 65mL:0.06 ~ 0.11mol; Temperature of reaction is 30 ~ 80 DEG C, and the reaction times is 10 ~ 48h.
When Lewis acid is aluminum chloride, trieline, tetracol phenixin, lewis acidic add-on are preferably 30mL:50 ~ 65mL:8 ~ 10g, best employing 30mL:65mL:10g; Temperature of reaction is preferably 60 ~ 80 DEG C (best employings 80 DEG C), and the reaction times is that 24 ~ 48h(the best selects 24h).
When Lewis acid is zinc chloride, trieline, tetracol phenixin, lewis acidic add-on are preferably 30mL:50 ~ 65mL:12 ~ 14g, best employing 30mL:65mL:14g; Described temperature of reaction is 60 ~ 80 DEG C (best employings 80 DEG C), and the reaction times is that 24 ~ 48h(the best selects 24h).
When Lewis acid is tin tetrachloride, trieline, tetracol phenixin, lewis acidic add-on are preferably 30mL:50 ~ 65mL:15.63 ~ 20g, best employing 30mL:65mL:20g; Temperature of reaction is 60 ~ 80 DEG C (best employings 60 DEG C), and the reaction times is that 10 ~ 48h(the best selects 48h).
Get electrophilic addition reaction complete after reaction solution, with distilled water extraction 2 ~ 3 times, after getting organic layer drying, distill out excessive tetracol phenixin, then underpressure distillation, obtain white crystal and be described heptachloropropane.
The present invention has the following advantages compared to existing technology: employing Lewis acid is catalyzer, and catalytic efficiency is high, decreases the reaction times, improves productive rate, and easy and safe to operate, environmentally friendly, and equipment is simple, is applicable to continuously a large amount of production.
Accompanying drawing explanation
Fig. 1 is the chemical equation of the preparation method of heptachloropropane of the present invention;
Fig. 2 is the infared spectrum of heptachloropropane prepared by the present invention.
Embodiment
Below in conjunction with specific embodiment, the preparation method to heptachloropropane of the present invention is described in detail.
Embodiment 1
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the catalyzer (aluminum trichloride (anhydrous)) of 8g.At 60 DEG C of temperature, reflux 10h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 79.86g, productive rate is 84.1%.
Embodiment 2-27
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the aluminum trichloride (anhydrous) as catalyzer, the reaction times is 10 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 8 | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 56.98 | 82.71 | 81.67 | 60.12 | 84.09 | 68.85 | 54.18 | 80.29 | 56.50 | 49.6 |
Productive rate/% | 60 | 87.1 | 86 | 63.31 | 88.55 | 72.5 | 50.06 | 84.85 | 59.5 | 52.2 |
Embodiment | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 | 8 |
Temperature of reaction DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 79.67 | 80.68 | 59.79 | 82.35 | 61.25 | 49.99 | 78.98 | 76.44 | 63.76 | 85.5 |
Productive rate/% | 83.9 | 84.96 | 62.96 | 86.72 | 64.5 | 52.64 | 83.17 | 80.5 | 67.14 | 90.0 |
Embodiment | 22 | 23 | 24 | 25 | 26 | 27 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 10 | 10 | 10 | 12 | 12 | 12 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 85.69 | 65.36 | 86.13 | 71.27 | 59.15 | 84.36 |
Productive rate/% | 90.23 | 68.83 | 90.7 | 70.05 | 62.29 | 88.84 |
Embodiment 28
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the aluminum trichloride (anhydrous) of 8g.At 60 DEG C of temperature, reflux 24h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 81.76g, productive rate is 86.1%.
Embodiment 29-54
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the aluminum trichloride (anhydrous) as catalyzer, the reaction times is 24 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 8 | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 67.13 | 88.1 | 85.13 | 67.14 | 88.2 | 75.23 | 65.25 | 86.15 | 67.45 | 56.6 |
Productive rate/% | 70.69 | 92.78 | 89.65 | 70.7 | 92.88 | 79.22 | 68.7l | 90.72 | 71.03 | 59.6 |
Embodiment | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 | 8 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 82.25 | 85.78 | 63.89 | 87.15 | 67.15 | 53.25 | 83.2 | 82..2 | 69.25 | 88.9 |
Productive rate/% | 86.61 | 90.33 | 67.28 | 91.78 | 70.71 | 56.08 | 87.61 | 87 | 72.93 | 93.6 |
Embodiment | 49 | 50 | 51 | 52 | 53 | 54 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 10 | 10 | 10 | 12 | 12 | 12 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 88.45 | 71.84 | 88.93 | 75.56 | 67.23 | 87.38 |
Productive rate/% | 93.14 | 75.65 | 93.65 | 79.57 | 70.8 | 92.02 |
Embodiment 55
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the aluminum trichloride (anhydrous) of 8g.At 60 DEG C of temperature, reflux 48h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 84.42g, productive rate is 88.9%.
Embodiment 56-81
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the aluminum trichloride (anhydrous) as catalyzer, the reaction times is 48 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 56 | 57 | 58 | 59 | 60 | 61 | 62 | 63 | 64 | 65 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 8 | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 71.25 | 89.9 | 88.4 | 71.2 | 90.1 | 80.12 | 70.35 | 89.5 | 70.3 | 60.14 |
Productive rate/% | 75.03 | 94.67 | 93.09 | 74.98 | 94.88 | 84.37 | 74.08 | 94.25 | 74.1 | 63.33 |
Embodiment | 66 | 67 | 68 | 69 | 70 | 71 | 72 | 73 | 74 | 75 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8 | 10 | 10 | 10 | 12 | 12 | 12 | 8 | 8 | 8 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 85.3 | 88.34 | 66.13 | 89.32 | 71.5 | 56.71 | 86.13 | 84.98 | 71.62 | 90.5 |
Productive rate/% | 89.83 | 93.03 | 69.64 | 94.06 | 75.29 | 59.72 | 90.7 | 89.49 | 75.42 | 95.3 |
Embodiment | 76 | 77 | 78 | 79 | 80 | 81 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 10 | 10 | 10 | 12 | 12 | 12 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 89.15 | 75.82 | 89.6 | 76.57 | 75.69 | 89.49 |
Productive rate/% | 93.88 | 79.84 | 94.36 | 80.63 | 79.71 | 94.24 |
Embodiment 82
In four-necked bottle, put into one piece of magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the zinc chloride of 8.2g.At 60 DEG C of temperature, reflux 10h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 66.47g, productive rate is 70.0%.
Embodiment 83-108
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the zinc chloride as catalyzer, the reaction times is 10 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 83 | 84 | 85 | 86 | 87 | 88 | 89 | 90 | 9192 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 5035 |
Catalyzer/g | 8.2 | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.28.2 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 3030 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 1010 |
Product quality/g | 56.79 | 77.68 | 79.2 | 62.54 | 80.35 | 80.24 | 63.23 | 80.56 | 48.6239.1 |
Productive rate/% | 59.8 | 81.8 | 83.4 | 65.86 | 84.61 | 84.5 | 66.58 | 84.84 | 51.241.2 |
Embodiment | 93 | 94 | 95 | 96 | 97 | 98 | 99 | 100 | 101 | 102 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.2 | 8.2 | 8.2 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 61.35 | 51.26 | 42.35 | 62.95 | 52.01 | 43.15 | 63.25 | 74.92 | 61.15 | 80.3 |
Productive rate/% | 64.61 | 53.98 | 44.6 | 66.29 | 54.77 | 45.44 | 66.6 | 78.9 | 64.39 | 84.5 |
Embodiment | 103 | 104 | 105 | 106 | 107 | 108 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 12 | 12 | 12 | 14 | 14 | 14 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 80.14 | 69.52 | 85.91 | 80.51 | 71.91 | 89.14 |
Productive rate/% | 84.39 | 73.21 | 90.47 | 84.78 | 75.73 | 93.87 |
Embodiment 109
In four-necked bottle, put into one piece of magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the zinc chloride of 8.2g.At 60 DEG C of temperature, reflux 24h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 78.15g, productive rate is 82.3%.
Embodiment 110-135
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the zinc chloride as catalyzer, the reaction times is 24 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 110 | 111 | 112 | 113 | 114 | 115 | 116 | 117 | 118 | 119 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 8.2 | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.2 | 8.2 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 65.12 | 86.13 | 90.13 | 71.14 | 89.12 | 90.23 | 75.55 | 91.15 | 75.42 | 64.8 |
Productive rate/% | 68.58 | 90.7 | 94.91 | 74.92 | 93.85 | 95.02 | 79.56 | 95.99 | 79.42 | 68.2 |
Embodiment | 120 | 121 | 122 | 123 | 124 | 125 | 126 | 127 | 128 | 129 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.2 | 8.2 | 8.2 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 80.25 | 83.89 | 70.19 | 84.15 | 83.99 | 73.31 | 86.2 | 82.62 | 71.25 | 89.9 |
Productive rate/% | 84.51 | 88.34 | 73.92 | 88.62 | 88.45 | 77.2 | 90.78 | 87.01 | 75.03 | 94.6 |
Embodiment | 130 | 131 | 132 | 133 | 134 | 135 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 12 | 12 | 12 | 14 | 14 | 14 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 91.01 | 72.67 | 90.91 | 91.51 | 77.94 | 92.01 |
Productive rate/% | 95.84 | 76.53 | 95.74 | 96.37 | 82.08 | 96.89 |
Embodiment 136
In four-necked bottle, put into one piece of magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the zinc chloride of 8.2g.At 60 DEG C of temperature, reflux 48h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 79.86g, productive rate is 84.1%.
Embodiment 137-162
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the zinc chloride as catalyzer, the reaction times is 48 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 137 | 138 | 139 | 140 | 141 | 142 | 143 | 144 | 145 | 146 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 8.2 | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.2 | 8.2 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 67.02 | 87.91 | 91.02 | 72.91 | 90.01 | 91.12 | 76.15 | 91.95 | 76.91 | 65.12 |
Productive rate/% | 70.58 | 92.58 | 95.85 | 76.78 | 94.78 | 95.96 | 80.19 | 96.83 | 80.99 | 68.57 |
Embodiment | 147 | 148 | 149 | 150 | 151 | 152 | 153 | 154 | 155 | 156 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 8.2 | 12 | 12 | 12 | 14 | 14 | 14 | 8.2 | 8.2 | 8.2 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 81.31 | 84.54 | 72.01 | 85.24 | 84.12 | 73.98 | 87.55 | 83.45 | 72.31 | 91.2 |
Productive rate/% | 85.63 | 89.03 | 75.83 | 89.76 | 88.58 | 77.91 | 92.2 | 87.88 | 76.15 | 96.1 |
Embodiment | 157 | 158 | 159 | 160 | 161 | 162 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 12 | 12 | 12 | 14 | 14 | 14 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 92.21 | 73.14 | 91.11 | 92.41 | 74.15 | 92.41 |
Productive rate/% | 97.1 | 77.02 | 95.95 | 97.31 | 78.08 | 97.31 |
Embodiment 163
In the four-necked bottle being placed with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g.At 60 DEG C of temperature, reflux 10h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 80.81g, productive rate is 85.1%.
Embodiment 164-189
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the tin tetrachloride as catalyzer, the reaction times is 10 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 164 | 165 | 166 | 167 | 168 | 169 | 170 | 171 | 172 | 173 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 15.63 | 15.63 | 18 | 18 | 18 | 20 | 20 | 20 | 15.63 | 15.63 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 56.31 | 82.81 | 84.61 | 61.32 | 86.13 | 84.42 | 60.98 | 85.82 | 52.32 | 32.13 |
Productive rate/% | 59.3 | 87.2 | 89.1 | 64.57 | 90.7 | 88.9 | 64.22 | 90.37 | 55.1 | 33.83 |
Embodiment | 174 | 175 | 176 | 177 | 178 | 179 | 180 | 181 | 182 | 183 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 15.63 | 18 | 18 | 18 | 20 | 20 | 20 | 15.63 | 15.63 | 15.63 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 59.83 | 61.24 | 39.65 | 61.3 | 59.35 | 39.12 | 59.31 | 80.53 | 55.31 | 81.83 |
Productive rate/% | 63 | 64.49 | 41.75 | 64.55 | 62.5 | 41.2 | 62.46 | 84.8 | 58.24 | 86.17 |
Embodiment | 184 | 185 | 186 | 187 | 188 | 189 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 18 | 18 | 18 | 20 | 20 | 20 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 10 | 10 | 10 | 10 | 10 | 10 |
Product quality/g | 83.59 | 60.42 | 85.98 | 83.24 | 59.41 | 84.13 |
Productive rate/% | 88.03 | 63.63 | 90.54 | 87.66 | 62.56 | 88.59 |
Embodiment 190
In the four-necked bottle being placed with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g.At 60 DEG C of temperature, reflux 24h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C) finally obtains white crystal 83.66g, and productive rate is 88.1%.
Embodiment 191-216
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the tin tetrachloride as catalyzer, the reaction times is 24 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 191 | 192 | 193 | 194 | 195 | 196 | 197 | 198 | 199 | 200 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 15.63 | 15.63 | 18 | 18 | 18 | 20 | 20 | 20 | 15.63 | 15.63 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 59.12 | 84.24 | 85.97 | 63.41 | 88.12 | 85.32 | 62.13 | 87.14 | 55.19 | 34.8 |
Productive rate/% | 62.26 | 88.71 | 90.53 | 66.77 | 92.8 | 89.85 | 65.43 | 91.76 | 58.12 | 36.65 |
Embodiment | 201 | 202 | 203 | 204 | 205 | 206 | 207 | 208 | 209 | 210 |
Tetracol phenixin/ml | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 15.63 | 18 | 18 | 18 | 20 | 20 | 20 | 15.63 | 15.63 | 15.63 |
Temperature of reaction/DEG C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 60.25 | 61.89 | 40.24 | 61.98 | 60.21 | 39.89 | 60.21 | 82.62 | 57.48 | 83.12 |
Productive rate/% | 63.45 | 65.17 | 42.38 | 65.27 | 63.4 | 42.20 | 63.41 | 87.01 | 60.53 | 87.53 |
Embodiment | 211 | 212 | 213 | 214 | 215 | 216 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 18 | 18 | 18 | 20 | 20 | 20 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 24 | 24 | 24 | 24 | 24 | 24 |
Product quality/g | 85.21 | 61.98 | 87.02 | 85.11 | 61.94 | 86.41 |
Productive rate/% | 89.73 | 65.27 | 91.64 | 89.63 | 65.23 | 91 |
Embodiment 217:
In the four-necked bottle being placed with magnetic stir bar, add the trieline of 30ml, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g.At 60 DEG C of temperature, reflux 48h.Then, reaction solution is poured in 200ml water, stir 5-10min, then separatory, and organic layer distilled water is cleaned three times, finally by organic over anhydrous Na
2sO
4dry.Subsequently by dried reaction solution at 77 DEG C, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, collect the cut that temperature is 74 DEG C-77 DEG C), then underpressure distillation, steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, collects the cut that temperature is 45 DEG C-50 DEG C).Finally obtain white crystal 86.51g, productive rate is 91.1%.
Embodiment 218-243
In the four-necked bottle being added with magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and the tin tetrachloride as catalyzer, the reaction times is 48 hours, and add-on, reaction times and productive rate see the following form respectively:
Embodiment | 218 | 219 | 220 | 221 | 222 | 223 | 224 | 225 | 226 | 227 |
Tetracol phenixin/ml | 35 | 65 | 50 | 35 | 65 | 50 | 35 | 65 | 50 | 35 |
Catalyzer/g | 15.63 | 15.63 | 18 | 18 | 18 | 20 | 20 | 20 | 15.63 | 15.63 |
Temperature of reaction/DEG C | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 30 | 30 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 63.02 | 87.91 | 87.13 | 66.21 | 89.98 | 87.11 | 65.01 | 89.51 | 58.21 | 37.89 |
Productive rate/% | 66.36 | 92.58 | 91.75 | 69.72 | 94.76 | 91.73 | 68.46 | 94.26 | 61.3 | 39.9 |
Embodiment tetracol phenixin/ml catalyzer/g temperature of reaction/DEG C reaction times product quality/g productive rate/% | 2286515.63304863.3166.67 | 2295018304864.5567.98 | 2303518304843.0145.29 | 2316518304864.3167.72 | 2325020304863.1966.54 | 2333520304842.9245.2 | 2346520304863.4166.78 | 2355015.63804885.1989.71 | 2363515.63804860.8164.04 | 2376515.63804886.3190.89 |
Embodiment | 238 | 239 | 240 | 241 | 242 | 243 |
Tetracol phenixin/ml | 50 | 35 | 65 | 50 | 35 | 65 |
Catalyzer/g | 18 | 18 | 18 | 20 | 20 | 20 |
Temperature of reaction/DEG C | 80 | 80 | 80 | 80 | 80 | 80 |
Reaction times | 48 | 48 | 48 | 48 | 48 | 48 |
Product quality/g | 87.91 | 65.01 | 90.13 | 87.41 | 64.15 | 89.81 |
Productive rate/% | 92.58 | 68.46 | 94.91 | 92.05 | 67.55 | 94.58 |
Claims (8)
1. a preparation method for heptachloropropane, is characterized in that: described heptachloropropane adopts trieline and tetracol phenixin to be raw material, is catalyzer, is prepared by electrophilic addition reaction with Lewis acid; Described Lewis acid is selected from aluminum chloride, zinc chloride or tin tetrachloride; Described trieline, tetracol phenixin, lewis acidic add-on are 30mL:35 ~ 65mL:0.06 ~ 0.11mol; Described temperature of reaction is 30 ~ 80 DEG C, and the reaction times is 10 ~ 48h; Chemical equation prepared by described heptachloropropane is:
。
2. preparation method according to claim 1, is characterized in that: described Lewis acid is aluminum chloride; Described trieline, tetracol phenixin, lewis acidic add-on are 30mL:50 ~ 65mL:8 ~ 10g; Described temperature of reaction is 60 ~ 80 DEG C, and the reaction times is 24 ~ 48h.
3. preparation method according to claim 2, is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:10g; Described temperature of reaction is 80 DEG C, and the reaction times is 24h.
4. preparation method according to claim 1, is characterized in that: described Lewis acid is zinc chloride; Described trieline, tetracol phenixin, lewis acidic add-on are 30mL:50 ~ 65mL:12 ~ 14g; Described temperature of reaction is 60 ~ 80 DEG C, and the reaction times is 24 ~ 48h.
5. preparation method according to claim 4, is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:14g; Described temperature of reaction is 80 DEG C, and the reaction times is 24h.
6. preparation method according to claim 1, is characterized in that: described Lewis acid is tin tetrachloride; Described trieline, tetracol phenixin, lewis acidic add-on are 30mL:50 ~ 65mL:15.63 ~ 20g; Described temperature of reaction is 60 ~ 80 DEG C, and the reaction times is 10 ~ 48h.
7. preparation method according to claim 6, is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:20g; Described temperature of reaction is 60 DEG C, and the reaction times is 48h.
8., according to the arbitrary described preparation method of claim 1 to 7, it is characterized in that: get described electrophilic addition reaction complete after reaction solution, with distilled water extraction 2 ~ 3 times, get organic over anhydrous Na
2sO
4after drying, distill out excessive tetracol phenixin, then underpressure distillation, obtain white crystal and be described heptachloropropane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310270566.1A CN103319302B (en) | 2013-06-28 | 2013-06-28 | Preparation method of heptachloropropane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310270566.1A CN103319302B (en) | 2013-06-28 | 2013-06-28 | Preparation method of heptachloropropane |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103319302A CN103319302A (en) | 2013-09-25 |
CN103319302B true CN103319302B (en) | 2015-07-01 |
Family
ID=49188401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310270566.1A Expired - Fee Related CN103319302B (en) | 2013-06-28 | 2013-06-28 | Preparation method of heptachloropropane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103319302B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102040586A (en) * | 2010-11-10 | 2011-05-04 | 兰州安杰利生物化学科技有限公司 | Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone |
JP2012254943A (en) * | 2011-06-07 | 2012-12-27 | Tokuyama Corp | Method for producing polychloropropene |
CN102964205A (en) * | 2012-12-17 | 2013-03-13 | 南京信息工程大学 | One-kettle way preparation method of 2-hydro-1,1,1,2,3,3,3-heptachloropropane |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5326913A (en) * | 1991-06-14 | 1994-07-05 | Daikin Industries Ltd. | Process for preparing fluorinated compound |
DE60323994D1 (en) * | 2002-08-22 | 2008-11-20 | Du Pont | PROCESS FOR PREPARING 2-CHLORO-1,1,1,2,3,3,3-HEPTAFLUORPROPAN, HEXAFLUORPROPEN AND 1,1,1,2,3,3,3-HEPTAFLUORPROPANE |
-
2013
- 2013-06-28 CN CN201310270566.1A patent/CN103319302B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102040586A (en) * | 2010-11-10 | 2011-05-04 | 兰州安杰利生物化学科技有限公司 | Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone |
JP2012254943A (en) * | 2011-06-07 | 2012-12-27 | Tokuyama Corp | Method for producing polychloropropene |
CN102964205A (en) * | 2012-12-17 | 2013-03-13 | 南京信息工程大学 | One-kettle way preparation method of 2-hydro-1,1,1,2,3,3,3-heptachloropropane |
Non-Patent Citations (1)
Title |
---|
卤素衍生物与烯属烃之化合作用;人风 等;《化学世界》;第9卷;19540123;第9卷(第1期);第23-26页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103319302A (en) | 2013-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
MY165914A (en) | Fire-extinguishing composition comprising organic acid compound | |
MY169444A (en) | Fire extinguishing composition generating fire extinguishing substance through high-temperature decomposition | |
CN101890360B (en) | Method for preparing novel catalyst used for hydrochlorination of acetylene | |
CN104072805B (en) | A kind of preparation method of composite flame-retardant agent based on Vermiculitum | |
CN102872904B (en) | Method for preparing shape-selective catalyst | |
MY175587A (en) | Fire extinguishing composition containing saccharide and saccharide derivative | |
CN104552514A (en) | Layered zirconium phosphate/ammonium polyphosphate composite flame retardant and preparation method thereof | |
MX340968B (en) | Fire extinguishing composition producing fire extinguishing substance by high temperature sublimation. | |
CN102258836B (en) | Flame-retarding fire extinguishing agent for coal mines | |
CN103319302B (en) | Preparation method of heptachloropropane | |
CN104258532A (en) | ABC ultrafine dry powder extinguishing agent and preparation method thereof | |
CN109019593A (en) | A kind of discarded ion exchange resin matrix activated carbon and the preparation method and application thereof | |
US20180361186A1 (en) | Fire-Extinguishing Composition | |
CN102949803B (en) | A kind of fire-extinguishing composite | |
CN104117262A (en) | Drawer type tail gas purification device | |
CN106008584A (en) | Method for controlling carborane derivative structure by click reaction | |
CN103665992A (en) | Flame-retardant paint composition | |
CN204208444U (en) | A kind of Chlorcosane tail gas treatment system | |
CN106423299A (en) | Preparation method for functional foam carbon for photo-catalytically degrading formaldehyde | |
CN104353438A (en) | Compound type carbon dioxide adsorbing agent and preparation method thereof | |
CN103550900A (en) | Super absorbent flame retardant fire extinguishing agent for inflammables | |
CN107841357A (en) | A kind of military high energy alcohol-based fuel additive and preparation method thereof | |
CN102018286A (en) | Cigarette filter additive for selectively reducing hydrocyanic acid in cigarette mainstream smoke, preparation and application | |
CN103550899A (en) | Super absorbent flame retardant fire extinguishing agent for storage | |
CN108245820A (en) | A kind of fire-extinguishing composite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150701 Termination date: 20180628 |