CN103319302A - Preparation method of heptachloropropane - Google Patents

Preparation method of heptachloropropane Download PDF

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Publication number
CN103319302A
CN103319302A CN2013102705661A CN201310270566A CN103319302A CN 103319302 A CN103319302 A CN 103319302A CN 2013102705661 A CN2013102705661 A CN 2013102705661A CN 201310270566 A CN201310270566 A CN 201310270566A CN 103319302 A CN103319302 A CN 103319302A
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reaction
tetracol phenixin
temperature
trieline
preparation
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CN103319302B (en
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张超智
李世娟
张君仪
费中彬
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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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

A kind of preparation method of heptachloropropane
Technical field
The present invention relates to a kind of preparation method of heptachloropropane.
Background technology
The tradition powder extinguishing agent mainly is comprised of activity fire extinguishing component, hydrophobic ingredient, inert filler.Hydrophobic ingredient mainly contains silicone oil and hydrophobic silicic aerogels; Inert filler is of a great variety, mainly plays anti-jolt ramming, caking, improves the dry powder exercise performance, the effects such as common appearance of the silicone oil polymerization of catalysis dry powder and improvement and fire foam.This quasi-tradition powder extinguishing agent has at home and abroad obtained very generally to use at present.
The tradition halon extinguishing agent, the halogen ion in the molecule helps 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 class fire-fighting medium mainly is that halogen ion damaged fuel produces hydrionic chain chemical reaction in combustion processes, interrupts burning and reaches the purpose of fire extinguishing.Various inflammable, combustible liquid fires and electrical equipment fire are applicable to put out a fire to save life and property.
At present, 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane are the analogues of powder type fire extinguisher main raw, are difficult to burning, and density should be solid-state under the normal temperature greater than water, can slowly decompose in air, does not stay residue after the vaporization, has good gas phase electrical insulating property.Traditional method adopts trieline and carbon tetrachloride reaction to prepare heptachloropropane, long reaction time, and productive rate is low, therefore need to seek a kind of effective catalyzer and improve reaction efficiency.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, to provide a kind of reaction efficiency high heptachloropropane preparation method.
In order to achieve the above object, the invention provides a kind of preparation method of heptachloropropane, adopting trieline and tetracol phenixin is raw material, take Lewis acid as catalyzer, prepares 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 ℃, and the reaction times is 10～48h.
When Lewis acid was aluminum chloride, trieline, tetracol phenixin, lewis acidic add-on were preferably 30mL:50～65mL:8～10g, the best 30mL:65mL:10g that adopts; Temperature of reaction is preferably 60～80 ℃ (80 ℃ of best employings), and the reaction times is that 24～48h(the best is selected 24h).
When Lewis acid was zinc chloride, trieline, tetracol phenixin, lewis acidic add-on were preferably 30mL:50～65mL:12～14g, the best 30mL:65mL:14g that adopts; Described temperature of reaction is 60～80 ℃ (80 ℃ of best employings), and the reaction times is that 24～48h(the best is selected 24h).
When Lewis acid was tin tetrachloride, trieline, tetracol phenixin, lewis acidic add-on were preferably 30mL:50～65mL:15.63～20g, the best 30mL:65mL:20g that adopts; Temperature of reaction is 60～80 ℃ (60 ℃ of best employings), and the reaction times is that 10～48h(the best is selected 48h).
Reaction solution after getting electrophilic addition reaction and finishing, with distilled water extraction 2～3 times, get the organic layer drying after, distill out excessive tetracol phenixin, then underpressure distillation obtains white crystal and is described heptachloropropane.
The present invention has the following advantages compared to existing technology: the employing Lewis acid is catalyzer, and catalytic efficiency is high, has reduced the reaction times, has improved productive rate, and easy and safe to operate, and is environmentally friendly, and equipment is simple, is fit to continuously a large amount of production.
Description of drawings
Fig. 1 is the preparation method's of heptachloropropane of the present invention chemical equation;
Fig. 2 is the infared spectrum of the heptachloropropane for preparing of the present invention.
Embodiment
Preparation method to heptachloropropane of the present invention is elaborated below in conjunction with specific embodiment.
Embodiment 1
In being added with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the catalyzer of 8g (aluminum trichloride (anhydrous)) of 30ml.Under 60 ℃ of temperature, reflux 10h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 79.86g, productive rate is 84.1%.
Embodiment 2-27
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the aluminum trichloride (anhydrous) of catalyzer, the reaction times is 10 hours, 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/℃ 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 ℃ 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/℃ 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 being added with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the aluminum trichloride (anhydrous) of 8g of 30ml.Under 60 ℃ of temperature, reflux 24h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 81.76g, productive rate is 86.1%.
Embodiment 29-54
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the aluminum trichloride (anhydrous) of catalyzer, the reaction times is 24 hours, 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/℃ 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/℃ 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/℃ 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 being added with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the aluminum trichloride (anhydrous) of 8g of 30ml.Under 60 ℃ of temperature, reflux 48h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 84.42g, productive rate is 88.9%.
Embodiment 56-81
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the aluminum trichloride (anhydrous) of catalyzer, the reaction times is 48 hours, 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/℃ 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/℃ 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/℃ 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 trieline, the tetracol phenixin of 50ml and the zinc chloride of 8.2g of 30ml.Under 60 ℃ of temperature, reflux 10h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 66.47g, productive rate is 70.0%.
Embodiment 83-108
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the zinc chloride of catalyzer, the reaction times is 10 hours, 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/℃ 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/℃ 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/℃ 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 trieline, the tetracol phenixin of 50ml and the zinc chloride of 8.2g of 30ml.Under 60 ℃ of temperature, reflux 24h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 78.15g, productive rate is 82.3%.
Embodiment 110-135
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the zinc chloride of catalyzer, the reaction times is 24 hours, 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/℃ 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/℃ 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/℃ 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 trieline, the tetracol phenixin of 50ml and the zinc chloride of 8.2g of 30ml.Under 60 ℃ of temperature, reflux 48h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 79.86g, productive rate is 84.1%.
Embodiment 137-162
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the zinc chloride of catalyzer, the reaction times is 48 hours, 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/℃ 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/℃ 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/℃ 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 being placed with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g of 30ml.Under 60 ℃ of temperature, reflux 10h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 80.81g, productive rate is 85.1%.
Embodiment 164-189
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the tin tetrachloride of catalyzer, the reaction times is 10 hours, 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/℃ 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/℃ 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/℃ 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 being placed with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g of 30ml.Under 60 ℃ of temperature, reflux 24h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut) finally obtains white crystal 83.66g, and productive rate is 88.1%.
Embodiment 191-216
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the tin tetrachloride of catalyzer, the reaction times is 24 hours, 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/℃ 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/℃ 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/℃ 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 being placed with the four-necked bottle of magnetic stir bar, add trieline, the tetracol phenixin of 50ml and the tin tetrachloride of 15.63g of 30ml.Under 60 ℃ of temperature, reflux 48h.Then, reaction solution is poured in the 200ml water, stirred 5-10min, separatory then, and organic layer cleaned three times with distilled water, at last with the organic layer anhydrous Na 2SO 4Dry.Subsequently with dried reaction solution under 77 ℃, simple distillation, (pressure is 15.26kPa to steam excessive tetracol phenixin, the collection temperature is 74 ℃-77 ℃ cut), then underpressure distillation steams 2-hydrogen-1,1,1,2,3,3,3-heptachloropropane (pressure is 0.2kPa, and the collection temperature is 45 ℃-50 ℃ cut).Finally obtain white crystal 86.51g, productive rate is 91.1%.
Embodiment 218-243
In being added with the four-necked bottle of magnetic stir bar, add the trieline of 30ml, add tetracol phenixin and as the tin tetrachloride of catalyzer, the reaction times is 48 hours, 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/℃ 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/℃ 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/℃ 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 (9)

1. the preparation method of a heptachloropropane is characterized in that: it is raw material that described heptachloropropane adopts trieline and tetracol phenixin, take Lewis acid as catalyzer, prepares by electrophilic addition reaction; Described Lewis acid is selected from aluminum chloride, zinc chloride or tin tetrachloride.
2. preparation method according to claim 1, it is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:35～65mL:0.06～0.11mol; Described temperature of reaction is 30～80 ℃, and the reaction times is 10～48h.
3. preparation method according to claim 2, it 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 ℃, and the reaction times is 24～48h.
4. preparation method according to claim 3, it is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:10g; Described temperature of reaction is 80 ℃, and the reaction times is 24h.
5. preparation method according to claim 2, it 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 ℃, and the reaction times is 24～48h.
6. preparation method according to claim 5, it is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:14g; Described temperature of reaction is 80 ℃, and the reaction times is 24h.
7. preparation method according to claim 2, it 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 ℃, and the reaction times is 10～48h.
8. preparation method according to claim 7, it is characterized in that: described trieline, tetracol phenixin, lewis acidic add-on are 30mL:65mL:20g; Described temperature of reaction is 60 ℃, and the reaction times is 48h.
9. according to claim 1 to 8 arbitrary described preparation methods, it is characterized in that: get the reaction solution after described electrophilic addition reaction is finished, with distilled water extraction 2～3 times, after getting the organic layer drying, distill out excessive tetracol phenixin, then underpressure distillation obtains white crystal and is described heptachloropropane.
CN201310270566.1A 2013-06-28 2013-06-28 Preparation method of heptachloropropane Expired - Fee Related CN103319302B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2054408C1 (en) * 1991-06-14 1996-02-20 Дайкин Индастриз Лтд. Method for production of fluorinated compound
US20050222471A1 (en) * 2002-08-22 2005-10-06 Nappa Mario J Processes for the preparation of 2-chloro-1,1,1,2,3,3,3-heptafluoropropane, hexafluoropropene and 1,1,1,2,3,3,3-heptafluoropropane
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2054408C1 (en) * 1991-06-14 1996-02-20 Дайкин Индастриз Лтд. Method for production of fluorinated compound
US20050222471A1 (en) * 2002-08-22 2005-10-06 Nappa Mario J Processes for the preparation of 2-chloro-1,1,1,2,3,3,3-heptafluoropropane, hexafluoropropene and 1,1,1,2,3,3,3-heptafluoropropane
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)

* Cited by examiner, † Cited by third party
Title
人风 等: "卤素衍生物与烯属烃之化合作用", 《化学世界》, vol. 9, no. 1, 23 January 1954 (1954-01-23), pages 23 - 26 *

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