CN1268593C - Method for isomerizating 1,4-dichloro-2-butylenes from syn form to anti form - Google Patents
Method for isomerizating 1,4-dichloro-2-butylenes from syn form to anti form Download PDFInfo
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- CN1268593C CN1268593C CN 200410099211 CN200410099211A CN1268593C CN 1268593 C CN1268593 C CN 1268593C CN 200410099211 CN200410099211 CN 200410099211 CN 200410099211 A CN200410099211 A CN 200410099211A CN 1268593 C CN1268593 C CN 1268593C
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- butylene
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- 238000000034 method Methods 0.000 title claims abstract description 22
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical group ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 abstract 8
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 sulfhydryl compound Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for isomerizing 1, 4-dichloro-2-butylene to an anti form from a cis form. A mixture of cis-form 1, 4-dichloro-2-butylene and 1, 4-dichloro-2-butylene is used as main raw material, and the volume ratio of the cis-form 1, 4-dichloro-2-butylene to the 1, 4-dichloro-2-butylene is from 100:0 to 20:80.1 to 10 g of bromo-succinimide is added into every 100 ml of the mixture of cis-form 1, 4-dichloro-2-butylene and 1, 4-dichloro-2-butylene, and bromo-succinimide is used as a catalyst for reaction. The reaction temperature is from 0 to 90 DEG C, and the reaction time is from 0.5 to 8 hours. The method of the present invention has the advantages of simple operating condition, low cost and high yield of anti form 1, 4-dichloro-2-butylene finally generated.
Description
Technical field
The present invention relates to a kind ofly with 1,4-two chloro-2-butylene transfer the method for high-load trans body to from the cis body.
Background technology
Trans 1,4-two chloro-2-butylene are 2-vinyl cyclopropane-1 of synthetic high-purity content, important intermediate [Clarence E.Clark, Jr., the Cincinnati of 1-dicarboxylic acid methyl esters; Richard G.Fayter, Jr., Fairfield, US.Pat.4781807], also be Synthetic 2,7-dimethyl-1,3,5-heptantriene-1, the important intermediate of 8-dialdehyde [H.Pommer, Angew.Chem.72,911-915,1960].The muriate that can buy normally 1 at present, the cis of 4-two chloro-2-butylene, trans mixture, also contain simultaneously a small amount of 3, the isomer of 4-two chloro-1-butylene.Can be by rectification method with three kinds of compound separation, thus obtain trans 1,4-two chloro-2-butylene.But this sepn process meeting causes cost to improve greatly, and the cis 1 after separating, 4-two chloro-2-butylene and 3, and 4-two chloro-1-butylene also will further be handled, and are cumbersome, are unfavorable for producing in batches.
Existing by catalysis with cis 1, it is trans 1 that 4-two chloro-2-butylene are isomerizated into, the way of 4-two chloro-2-butylene has following four kinds of methods:
One, US 2911450 patents, the inorganic salt of selecting iron, copper for use are as catalyzer, cuprous chloride for example, iron trichloride;
Two, W.G.Niehaus, Jr., Bioorg.Chem., 3 (3), 302-10 (1974) and C.Walling, etal., J.Amer.Chem.Soc., 81,1144-8 (1959) selects for use sulfhydryl compound as catalyzer;
Three, N.p.Neureiter, etal., J.Amer.Chem.Soc., 82,5354-8 (1960) selects for use hydrogen bromide as catalyzer;
Four, in US Pat 4781807 (1988) patents, as catalyzer, be initiator with Diisopropyl azodicarboxylate or UV-light with anhydrous hydrogen bromide or mercaptoethanol.
More than in four kinds of methods, what preceding 3 kinds of methods finally obtained is 1, the equilibrium products of trans/cis=80/20 of 4-two chloro-2-butylene is therefore trans 1, the content of 4-two chloro-2-butylene is lower, purity can only reach 80%.Though method four finally obtains trans 1, the content of 4-two chloro-2-butylene is greater than 90%, but mercaptoethanol is very smelly, the health that is unfavorable for the operator during production, and mercaptoethanol boiling point and product, be trans 1,4-two chloro-2-butylene boiling points are very near, can only separate by WATER-WASHING METHOD, have greater environmental impacts; Anhydrous hydrogen bromide is a kind of severe corrosive acid, very easily human body is damaged, therefore very inconvenient in operating process, and because its severe corrosive, therefore require production unit to have quite high erosion resistance, this has just increased production cost, is unfavorable for producing in batches, more is unfavorable for carrying out market competition.
Summary of the invention
At the deficiencies in the prior art part, the invention provides a kind of output height, operational condition is simple, cost is low with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism.
The present invention is for reaching above purpose, be to realize: provide a kind of with 1 by such technical scheme, 4-two chloro-2-butylene turn to the method for trans body from cis isomerism, with cis-trans 1, the mixture of 4-two chloro-2-butylene is a main raw material, and cis and trans volume ratio are 100: 0～20: 80 in the described mixture; According to the ratio that the mixture of every 100ml adds 1～10g bromo-succinimide, select for use bromo-succinimide to react as catalyzer; Temperature of reaction is 0～90 ℃, and the reaction times is 0.5～8 hour.
As a kind of improvement of the present invention: earlier described mixture is dissolved in the solvent, adds bromo-succinimide again, the amount of solvent is 1～10 times of volume of mixture.
As a further improvement on the present invention: solvent is normal hexane, hexanaphthene or tetracol phenixin.
As a further improvement on the present invention: the ratio of adding 1～10g bromo-succinimide according to the mixture of every 100ml, select for use described bromo-succinimide to react as catalyzer, described temperature of reaction is 50～70 ℃, and the reaction times is 0.5～3 hour.
Of the present invention with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism, make catalyzer with bromo-succinimide.Bromo-succinimide is a kind of conventional industrial chemicals, buys easily; And it is stable solid-state, and no stink can not cause environmental pollution, can not endanger operator's health.In the production, operating equipment is not had the particularization requirement, operational condition is simple, only needs simple stirring, can finish reaction under common room temperature, the reaction conditions gentleness; If the certain temperature of being heated to can also shorten the reaction times.That adopts that method of the present invention finally makes is trans 1,4-two chloro-2-butylene purity height, can reach 〉=90%, color is that little Huang is to faint yellow; Can directly use, or straight run distillation can obtain colourless high-load product.
Embodiment
Embodiment 1, with 1 of 100ml, the cis-trans mixture of 4-two chloro-2-butylene and 1.2g bromo-succinimide carry out catalyzed reaction after mixing under 60 ℃ temperature, the reaction products therefrom is as shown in the table: (GC detection)
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (77.0/20.0 anti-/ suitable) |
| 15 minutes | (87.0/8.5 anti-/ suitable) |
| 30 minutes | (93.0/3.8 anti-/ suitable) |
After promptly 30 minutes, in the product of reaction gained, contain 93% trans 1,4-two chloro-2-butylene and 3.8% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 93%.
Example 2: with 1 of 100ml, the cis-trans mixture of 4-two chloro-2-butylene and 5.0g bromo-succinimide carry out catalyzed reaction after mixing under 55 ℃ temperature, and the reaction products therefrom is as shown in the table: (GC detection)
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (5.8/89.0 anti-/ suitable) |
| 15 minutes | (47.2/47.0 anti-/ suitable) |
| 30 minutes | (85.0/8.7 anti-/ suitable) |
| 60 minutes | (90.5/4.7 anti-/ suitable) |
After promptly 60 minutes, in the product of reaction gained, contain 90.5% trans 1,4-two chloro-2-butylene and 4.7% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 90.5%.
Example 3: with 1 of 100ml, the cis-trans mixture insulation of 4-two chloro-2-butylene is at 65 ℃, added the 1.0g bromo-succinimide every 10 minutes and mix, add the 7.0g bromo-succinimide altogether and carry out catalyzed reaction, reaction product is as shown in the table: (GC detection)
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 10 minutes | (78.2/18.4 anti-/ suitable) |
| 20 minutes | (85.5/10.6 anti-/ suitable) |
| 30 minutes | (91.1/5.7 anti-/ suitable) |
| 40 minutes | (91.5/5.4 anti-/ suitable) |
| 50 minutes | (92.1/4.5 anti-/ suitable) |
| 60 minutes | (92.1/4.6 anti-/ suitable) |
| 70 minutes | (92.2/4.5 anti-/ suitable) |
After promptly 70 minutes, in the product of reaction gained, contain 92.2% trans 1,4-two chloro-2-butylene and 4.5% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 92.2%.
Example 4: with 1 of 100ml, the cis-trans mixture of 4-two chloro-2-butylene is dissolved in the 100ml tetracol phenixin, adds the 6.0g bromo-succinimide, and insulation obtains following result (GC detection) at 75～80 ℃:
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (22.0/75.8 anti-/ suitable) |
| 30 minutes | (35.7/59.6 anti-/ suitable) |
| 60 minutes | (58.8/38.2 anti-/ suitable) |
| 90 minutes | (77.4/19.8 anti-/ suitable) |
| 120 minutes | (84.6/11.8 anti-/ suitable) |
| 150 minutes | (89.4/7.2 anti-/ suitable) |
| 180 minutes | (90.3/6.3 anti-/ suitable) |
| 360 minutes | (90.8/5.9 anti-/ suitable) |
After promptly 360 minutes, in the product of reaction gained, contain 90.8% trans 1,4-two chloro-2-butylene and 5.9% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 90.8%.
Example 5: with the cis 1 of 95ml, 4-two chloro-2-butylene, 5ml's is trans 1, and 4-two chloro-2-butylene and 1.3g bromo-succinimide react under 50 ℃ temperature after mixing, and reaction product is as shown in the table: (GC detection)
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (5.9/89.0 anti-/ suitable) |
| 15 minutes | (47.4/47.2 anti-/ suitable) |
| 30 minutes | (85.2/8.5 anti-/ suitable) |
| 60 minutes | (90.6/4.7 anti-/ suitable) |
After promptly 60 minutes, in the product of reaction gained, contain 90.6% trans 1,4-two chloro-2-butylene and 4.7% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 90.6%.
Example 6: trans 1 with 20ml, the cis 1 of 4-two chloro-2-butylene, 80ml, 4-two chloro-2-butylene are dissolved in the 900ml tetracol phenixin, add the 2.0g bromo-succinimide, and insulation obtains following result (GC detection) at 75 ℃:
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (22.0/75.8 anti-/ suitable) |
| 30 minutes | (58.8/38.2 anti-/ suitable) |
| 60 minutes | (77.4/20.1 anti-/ suitable) |
| 90 minutes | (85.4/11.8 anti-/ suitable) |
| 120 minutes | (92.2/5.2 anti-/ suitable) |
After promptly 120 minutes, in the product of reaction gained, contain 92.2% trans 1,4-two chloro-2-butylene and 5.2% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 92.2%.
Example 7: with the cis 1 of 95ml, 4-two chloro-2-butylene, 5ml's is trans 1, and 4-two chloro-2-butylene and 9.5g bromo-succinimide react under 50 ℃ temperature after mixing, and reaction product is as shown in the table: (GC detection)
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (5.9/89.0 anti-/ suitable) |
| 15 minutes | (45.4/48.2 anti-/ suitable) |
| 30 minutes | (85.2/8.5 anti-/ suitable) |
| 60 minutes | (91.6/4.3 anti-/ suitable) |
After promptly 60 minutes, in the product of reaction gained, contain 91.6% trans 1,4-two chloro-2-butylene and 4.3% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 91.6%.
Example 8: with 1 of 100ml, the cis-trans mixture of 4-two chloro-2-butylene is dissolved in the 100ml tetracol phenixin, adds the 6.0g bromo-succinimide, and insulation obtains following result (GC detection) at 5 ℃:
| Time | 1, the content (g/g) of the trans and cis of 4-two chloro-2-butylene |
| 0 minute | (22.0/75.8 anti-/ suitable) |
| 60 minutes | (35.7/59.6 anti-/ suitable) |
| 120 minutes | (56.3/37.2 anti-/ suitable) |
| 180 minutes | (76.5/19.6 anti-/ suitable) |
| 360 minutes | (85.6/11.8 anti-/ suitable) |
| 420 minutes | (89.4/7.2 anti-/ suitable) |
| 480 minutes | (90.5/5.6 anti-/ suitable) |
After promptly 480 minutes, in the product of reaction gained, contain 90.5% trans 1,4-two chloro-2-butylene and 5.6% cis 1,4-two chloro-2-butylene, trans 1, the purity of 4-two chloro-2-butylene is 90.5%.
More than the product that finally obtains of each embodiment, carry out corresponding operating with distillation method again, can improve trans 1, the purity of 4-two chloro-2-butylene.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1, a kind of with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism, and it is characterized in that: with cis-trans 1, the mixture of 4-two chloro-2-butylene is a main raw material, and cis and trans volume ratio are 100: 0～20: 80 in the described mixture; According to the ratio that the mixture of every 100ml adds 1～10g bromo-succinimide, select for use bromo-succinimide to react as catalyzer; Temperature of reaction is 0～90 ℃, and the reaction times is 0.5～8 hour.
2, according to claim 1 with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism, it is characterized in that: earlier described mixture is dissolved in the solvent, adds bromo-succinimide again, the amount of described solvent is 1～10 times of volume of mixture.
3, according to claim 2 with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism, and it is characterized in that: described solvent is normal hexane, hexanaphthene or tetracol phenixin.
4, according to claim 1 or 3 described with 1,4-two chloro-2-butylene turn to the method for trans body from cis isomerism, it is characterized in that: the ratio of adding 1～10g bromo-succinimide according to the mixture of every 100ml, select for use described bromo-succinimide to react as catalyzer, described temperature of reaction is 50～70 ℃, and the reaction times is 0.5～3 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410099211 CN1268593C (en) | 2004-12-29 | 2004-12-29 | Method for isomerizating 1,4-dichloro-2-butylenes from syn form to anti form |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099211 CN1268593C (en) | 2004-12-29 | 2004-12-29 | Method for isomerizating 1,4-dichloro-2-butylenes from syn form to anti form |
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| CN1660729A CN1660729A (en) | 2005-08-31 |
| CN1268593C true CN1268593C (en) | 2006-08-09 |
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| JP5655527B2 (en) * | 2009-12-02 | 2015-01-21 | 住友化学株式会社 | Process for producing (Z) -cyanoalkenylcyclopropanecarboxylic acid compound |
| CN102219637A (en) * | 2011-04-27 | 2011-10-19 | 浙江医药股份有限公司新昌制药厂 | Method for isomerizing 1,4-dichloro-2-butylene from cis-form to trans-form |
| CN110862292B (en) * | 2019-11-19 | 2021-04-06 | 中国科学院兰州化学物理研究所 | Preparation method of 1-aryl-1, 2-dibromoethane |
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