CN103319302B - Preparation method of heptachloropropane - Google Patents

Preparation method of heptachloropropane Download PDF

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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
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reaction
tetracol phenixin
temperature
trieline
add
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CN103319302A (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
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.
CN201310270566.1A 2013-06-28 2013-06-28 Preparation method of heptachloropropane Expired - Fee Related CN103319302B (en)

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