CN102875271B - Method for synthesizing chlorinated aromatic hydrocarbon with participation of trichloroisocyanuric acid - Google Patents
Method for synthesizing chlorinated aromatic hydrocarbon with participation of trichloroisocyanuric acid Download PDFInfo
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- CN102875271B CN102875271B CN201210401934.7A CN201210401934A CN102875271B CN 102875271 B CN102875271 B CN 102875271B CN 201210401934 A CN201210401934 A CN 201210401934A CN 102875271 B CN102875271 B CN 102875271B
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- trichloroisocyanuric acid
- aromatic hydrocarbons
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Abstract
The invention discloses a method for synthesizing chlorinated aromatic hydrocarbons with the participation of trichloroisocyanuric acid. The method comprises the following steps of: under the condition that acetonitrile is used as solvent, conducting chlorinating reaction on aromatic hydrocarbons by using inorganic salt as catalyst and trichloroisocyanuric acid as chlorination reagent, controlling temperature to be 70-90DEG C and time to be 1-24h during reaction, cooling products to room temperature after reaction, removing solids, and removing solvent acetonitrile by using a rotary evaporator to obtain the chlorinated aromatic hydrocarbons. For aromatic hydrocarbons with higher reaction activity, ammonium nitrate is used as catalyst; and for aromatic hydrocarbons with lower reaction activity, ferric chloride is used as catalyst. The method for synthesizing chlorinated aromatic hydrocarbons with the participation of trichloroisocyanuric acid has the advantages that safe and cheap compounds are used as chlorinating reagent, the pollutant emission during chlorinating reaction is reduced, the cheap and easy-to-obtain aromatic hydrocarbons are enabled to react under comparatively moderate conditions and the method has a potential in industrialized large-scale production.
Description
Technical field
The present invention relates to a kind of phenyl ring chlorination method, particularly a kind of synthetic method of take the chlorinated aromatic hydrocarbons compounds that trichloroisocyanuric acid is chlorinating agent, belongs to the technical field of preparation and the application of fine chemical product.
Background technology
Chlorinated aromatic compound is important organic synthesis intermediate, is widely used in the synthetic of the performance chemicalses such as medicine, agricultural chemicals.Chlorination is one of important foundation reaction in organic synthesis, the most traditional chlorinating agent is chlorine, utilize chlorine under alkaline condition, aromatics is had to an optionally chloro (H. Shimizu, K. Shimizu, N. Kubodera, T. Mikami, K. Tsuzaki, H. Suwa, K. Harada, A. Hiraide, M. Shimizu, K. Koyama, Y. Ichikawa, D. Hirasawa, Y. Kito, M. Kobayashi, M. Kigawa, M. Kato, T. Kozono, H. Tanaka, M. Tanabe, M. Iguchi and M. Yoshida,
org. Process Res. Dev., 2005,9,278.) but because chlorine toxicity is large, the difficult treatment such as transportation, production, the three wastes, its application is restricted day by day.
Thionyl chloride is also a kind of traditional chlorination reagent, and because its reactivity is higher, by product is gas, and it is convenient to process, so often by laboratory, used (F. Grein, A. C. Chen, D. Edwards and C. M. Crudden,
j. Org. Chem., 2006,71,861.), but reaction preference is poor, dichloro-product is more, and the productive rate of a chloro heptanone is only 59%, and byproduct gas toxicity is larger.
In addition, hypochlorous acid also has certain chlorization, therefore be also used to chlorination.Have bibliographical information, hypochlorous acid can with the addition reaction of 1-methyl cyclohexene generation chloro, thereby obtain the β-chloropharin (opening and closing victory, chemistry circular, 1991,11,21.) of ring-type.Reaction is carried out in methylene dichloride, and productive rate is higher, can reach 78%.Secondly, trimethylchlorosilane is also found to have chlorization, and for example, in methyl-sulphoxide (DMSO), trimethylchlorosilane and alcohol at room temperature the substitution reaction of hydroxyl can occur rapidly, and productive rate is 88～96%.（?D.?C.?Snyder,?
J.?Org.?Chem.,?1995,?60,?2638.?）。Again, the chlorination of chlorinated ketone is familiar with about cupric chloride by people gradually, and Hu Aixi etc. once reported: it can carry out Selective chlorination reaction to 6-methoxyl group-2-acyl-naphthaline in alcoholic solvent.This reaction is carried out under the condition of reflux, and the productive rate of chloro thing is the highest can reach 98%(Hu Aixi, the history Culture Revolution, Wang pioneer, Chen Ke, applied chemistry, 2004,21,174.).
Many traditional chlorinating agents are the part that haves much room for improvement such as toxic large, operation inconvenience all, and therefore the synthetic method of existing chlorinated aromatic hydrocarbons compounds also exists the shortcomings such as operation is safe not, reaction preference is lower, pollutant emission is more.
Summary of the invention
Object of the present invention provides a kind of synthetic method of chlorinated aromatic hydrocarbons compounds of trichloroisocyanuric acid participation in order to solve above-mentioned technical problem, with trichloroisocyanuric acid (trichloroisocyanuric acid, TCCA) be chlorinating agent, take inorganic salt as catalyzer, and the arene compounds of take synthesizes chlorinated aromatic hydrocarbons compounds as substrate carries out chlorination.This synthetic method has been used comparatively safe chlorinating agent, has reduced the discharge of pollutent, and arene compounds cheap and easy to get is reacted under comparatively gentle condition, has the potentiality of commercial scale production.
Technical scheme of the present invention
The synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid participates in, the reaction equation of its building-up process as shown in Figure 1, be that arene compounds is under the condition of acetonitrile existence, take inorganic salt as catalyzer, the trichloroisocyanuric acid of take carries out chlorination as chlorinating agent, arene compounds used, the consumption of trichloroisocyanuric acid and inorganic salt calculates in molar ratio, be arene compounds: trichloroisocyanuric acid: inorganic salt are 0.5～1.5:1:0.04～0.5, chlorination process control temp is 70～90 ℃, preferably 85 ℃, time 1～24h, after finishing, reaction is cooled to room temperature, solids removed by filtration, with Rotary Evaporators, remove solvent acetonitrile, obtain chlorinated aromatic hydrocarbons compounds,
Arene compounds in Fig. 1, wherein the R of functional group base is CH
3o-, C
2h
5o-, C
6h
5o-, C
6h
5-, CH
3-, C
2h
5-, Bn-or NO
2-.
In the synthetic method of the chlorinated aromatic hydrocarbons compounds participating at above-mentioned trichloroisocyanuric acid, because the electronic effect of the R of functional group base is different in arene compounds, make the activity of arene compounds chlorination also not identical:
When R base is CH
3o-, C
2h
5o-, C
6h
5o-, C
6h
5-, CH
3-, C
2h
5-, during Bn-, the reactive behavior of arene compounds is higher, with cheap ammonium nitrate (NH
4nO
3) as catalyzer, chlorination can carry out smoothly, wherein the consumption of arene compounds used, trichloroisocyanuric acid and ammonium nitrate calculates in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: NH
4nO
3for 1:1.2:0.04.
When R base is NO
2in-time, the reactive behavior of arene compounds is lower, must take iron(ic) chloride as catalyzer, and chlorination can occur, wherein arene compounds used, trichloroisocyanuric acid and iron(ic) chloride (FeCl
3) consumption calculate in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: FeCl
3for 1:1.2:0.5.
Beneficial effect of the present invention
The present invention is a kind of synthetic method of chlorinated aromatic hydrocarbons compounds of trichloroisocyanuric acid participation, because trichloroisocyanuric acid is a kind of solid chemical compound, easy to use, store easily, therefore, take that the chloro process that trichloroisocyanuric acid is chlorinating agent is more more convenient than the chloro process of traditional use chlorine, safety.
Further, although N-chlorosuccinimide (NCS) and two chlordantoins (DCDMH) are two kinds of existing solid chlorinating agents, also very conventional in chlorination, but compare with above-mentioned two kinds of chlorinating agents, trichloroisocyanuric acid has higher chlorinity, and the in the situation that of same molar, trichloroisocyanuric acid can provide more chlorion, the efficiency of chlorination is improved.On the other hand, in many organic reactions, trichloroisocyanuric acid is often used as cheap oxygenant and uses, and the present invention uses it for chlorination, has expanded the purposes of this cheap compound trichloroisocyanuric acid.
Further, the synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid of the present invention participates in, take simple inorganic salt as catalyzer.And existing chlorination often needs to use the special catalyzer such as solid-carried catalyst, these catalyst effect are excellent, but relatively costly, difficult acquisition.The present invention's simple inorganic salt catalyst used is cheap, very easily obtain, for chlorination also have smoothly a good catalytic effect, therefore, with simple inorganic salt, be the cost that catalyzer can effectively reduce chlorination, increase economic efficiency.
Further, the synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid of the present invention participates in, by product after trichloroisocyanuric acid generation chlorination is tricyanic acid, because tricyanic acid is at room temperature solid, can recycle, the synthetic method of the chlorinated aromatic hydrocarbons compounds that therefore a kind of trichloroisocyanuric acid of the present invention participates in has reduced the pollutant discharge amount in chlorination process, can efficent use of resources, reduce production costs.
In sum, that the synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid of the present invention participates in has is easy and simple to handle, chlorinating agent and catalyzer cheap and easy to get, reduced the advantages such as pollutant discharge amount, reaction times in chlorination process is relatively short, be more conducive to commercial scale production.
Embodiment
The general expression of the specific embodiment of the invention is: arene compounds substrate is dissolved in acetonitrile, add chlorinating agent trichloroisocyanuric acid and inorganic salt catalyst, reacting by heating, question response finishes, remove by filter insolubles, with Rotary Evaporators, remove solvent acetonitrile, through simple process, obtain chlorinated aromatic hydrocarbons compounds.
Because the difference of arene compounds chlorination activity, adopts different catalyzer, embodiment can be divided into mode A and mode B two classes.
Mode A: when arene compounds contains electron-donating group, chlorination activity is higher, selects ammonium nitrate as catalyzer.
Mode A embodiment is as follows:
Arene compounds is dissolved in acetonitrile, add catalyzer ammonium nitrate and chlorinating agent trichloroisocyanuric acid, chlorination is carried out in heating, it is 85 ℃ that reaction process is controlled temperature, time 1～12h, is cooled to room temperature, solids removed by filtration after reaction finishes, with Rotary Evaporators, remove solvent acetonitrile, obtain chlorinated aromatic hydrocarbons compounds.Wherein arene compounds used, trichloroisocyanuric acid and inorganic salt NH
4nO
3consumption calculate in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: NH
4nO
3=1:1.2:0.04.
In table 1, numbering 1 ~ 7 synthetic method used is mode A, is about to R base and is respectively CH
3o-, C
2h
5o-, C
6h
5o-, Bn-, C
6h
5-, CH
3-and C
2h
5-arene compounds respectively as substrate, using acetonitrile respectively as solvent, with ammonium nitrate catalyzer, with trichloroisocyanuric acid chlorinating agent, controlling respectively temperature is 85 ℃, time 1～12h carries out chlorination, after reaction finishes, is cooled to room temperature, solids removed by filtration, revolve and desolventize acetonitrile, obtain corresponding chlorinated aromatic hydrocarbons compounds;
The following examples 1 and embodiment 2 also belong to mode A.
Mode B: when arene compounds contains electron withdrawing group, chlorination activity is lower, selects iron(ic) chloride as catalyzer.
Mode B embodiment is as follows:
Arene compounds is dissolved in acetonitrile, adds catalyst Fe Cl
3with chlorinating agent trichloroisocyanuric acid, chlorination is carried out in heating, and it is 85 ℃ that reaction process is controlled temperature, and time 24h is cooled to room temperature after reaction finishes, and solids removed by filtration, removes solvent acetonitrile with Rotary Evaporators, obtains chlorinated aromatic hydrocarbons compounds.Wherein arene compounds used, trichloroisocyanuric acid and FeCl
3consumption calculate in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: FeCl
3=1:1.2:0.5.
In table 1, numbering 8 synthetic methods used are mode B, and being about to R base is NO
2-arene compounds as substrate, using acetonitrile as solvent, with FeCl
3for catalyzer, take trichloroisocyanuric acid as chlorinating agent, chlorination is carried out in heating, it is 85 ℃ that reaction process is controlled temperature, time 24h, is cooled to room temperature, solids removed by filtration after reaction finishes, with Rotary Evaporators, remove solvent acetonitrile, obtain corresponding chlorinated aromatic hydrocarbons compounds.
The following examples 3 also belong to mode B.
table 1, different arene compounds form the productive rate of chlorinated aromatic hydrocarbons compounds under trichloroisocyanuric acid effect
| Numbering | Substrate | Reaction times (h) | Chlorinated aromatic hydrocarbons compounds products collection efficiency (%) |
| 1 | R is CH 3The arene compounds of O- | 1 | 95 |
| 2 | R is C 2H 5The arene compounds of O- | 1 | 95 |
| 3 | R is C 6H 5The arene compounds of O- | 1 | 96 |
| 4 | R is the arene compounds of Bn- | 12 | 92 |
| 5 | R is C 6H 5-arene compounds | 12 | 92 |
| 6 | R is CH 3-arene compounds- | 12 | 91 |
| 7 | R is C 2H 5-arene compounds | 12 | 92 |
| 8 | R is NO 2-arene compounds | 24 | 90 |
Productive rate=the m of the chlorinated aromatic hydrocarbons compounds product described in table 1
1/ m
2* 100%.
M
1output for actual chlorinated aromatic hydrocarbons compounds; m
2for theoretical yield.
As can be seen from Table 1, for the arene compounds that contains electron-donating group, ammonium nitrate has good katalysis, by the chlorination of trichloroisocyanuric acid, can obtain smoothly corresponding chlorinated aromatic hydrocarbons compounds.For the arene compounds that contains electron withdrawing group, use iron(ic) chloride just can play katalysis, by the chlorination of trichloroisocyanuric acid, also can obtain corresponding chlorinated aromatic hydrocarbons compounds.
In sum, arene compounds substrate for different activities, adopt different simple inorganic salt as catalyzer, take trichloroisocyanuric acid as chlorinating agent, pass through chlorination, can obtain corresponding chlorinated aromatic hydrocarbons compounds, this corresponding chlorinated aromatic hydrocarbons compounds productive rate is 90 ~ 96%.
Below by specific embodiment, the present invention is further set forth, but do not limit the present invention.
In various embodiments of the present invention, relevant information raw materials used, reagent is as follows:
Trichloroisocyanuric acid, CP, Chemical Reagent Co., Ltd., Sinopharm Group;
Ammonium nitrate, CP, Shanghai reagent one factory;
Iron(ic) chloride, CP, Shanghai reagent one factory;
Acetonitrile, CP, Chemical Reagent Co., Ltd., Sinopharm Group;
Methyl-phenoxide, CP, Chemical Reagent Co., Ltd., Sinopharm Group;
Phenyl ether, CP, Chemical Reagent Co., Ltd., Sinopharm Group;
Oil of mirbane, CP, Chemical Reagent Co., Ltd., Sinopharm Group.
In various embodiments of the present invention, the relevant information of detecting instrument used and equipment is as follows:
Melting point compound is measured by Yanano MP 500 microscope melting point apparatus, and temperature is not calibrated;
RE-52C type Rotary Evaporators, is produced by Qingpu Shanghai Hu Xi instrument plant;
1h NMR spectrogram, by varian INOVA-500 type nmr determination, is inside designated as tetramethylsilane (TMS).
embodiment 1
In the three-necked bottle of magnetic stir bar, reflux condensing tube is housed, adding 1.08g(10 mmol) (wherein R base is CH to methyl-phenoxide
3-), 2.79g(12mmol) trichloroisocyanuric acid, 0.032g(0.4mmol) ammonium nitrate, 30mL acetonitrile, be warming up to 85 ℃, reaction 1h, stopped reaction, be chilled to room temperature, solids removed by filtration, removes after solvent acetonitrile to obtain 1.35g colourless oil liquid 4-chloroneb, productive rate: 95% with Rotary Evaporators.Boiling point: 199-201 ℃ (101KPa) (literature value: 199-201 ℃ (101KPa)).After testing, the physical data of product all approaches literature value.
Through magnetic resonance detection, obtain hydrogen spectrum data, to characterize product structure.Concrete data are as follows:
1H?NMR?(CDCl
3,?500?MHz)?δ:?3.84?(s,?3H,?OCH
3),?6.81?(d,?
J=7.6?Hz,?2H,?ArH),?7.27?(d,?
J=7.6?Hz,?2H,?ArH)。
embodiment 2
In the three-necked bottle of magnetic stir bar, reflux condensing tube is housed, adding 1.70g(10 mmol) (wherein R base is C to phenyl ether
6h
5o-), 2.79g(12 mmol) trichloroisocyanuric acid, 0.032g(0.4 mmol) ammonium nitrate, 30mL acetonitrile, be warming up to 85 ℃, reaction 1h, stopped reaction, be chilled to room temperature, solids removed by filtration, removes after solvent acetonitrile to obtain 1.96g colourless oil liquid 4-chlorodiphenyl ether with Rotary Evaporators.Productive rate: 96%.Boiling point: 283-285 ℃ (101KPa) (literature value: 283-285 ℃ (101KPa))
Through magnetic resonance detection, obtain hydrogen spectrum data, to characterize product structure.Concrete data are as follows:
1H?NMR?(CDCl
3,?500?MHz)?δ:?6.90?(d,?
J=8.0?Hz,?2H,?ArH),?6.99-7.05?(m,?3H,?ArH),?7.30-7.33?(m,?2H,?ArH),?7.43?(d,?
J=8.0?Hz,?2H,?ArH)。
embodiment 3
In the three-necked bottle of magnetic stir bar, reflux condensing tube is housed, adding 1.23g(10mmol) (wherein R base is NO to oil of mirbane
2-), 2.79g(12mmol) trichloroisocyanuric acid, 0.81g(5mmol) iron(ic) chloride, 30mL acetonitrile, be warming up to 85 ℃, reaction 24h, stopped reaction, is chilled to room temperature.Solids removed by filtration, revolves and desolventizes after acetonitrile to obtain 1.42g solid 3-chloronitrobenzene.Productive rate: 90%.Fusing point: 44-45 ℃ (literature value: 46 ℃)
Through magnetic resonance detection, obtain hydrogen spectrum data, to characterize product structure.Concrete data are as follows:
1H?NMR?(CDCl
3,?500?MHz)?δ:?7.53-7.55?(m,?1H,?ArH),?7.68-7.70?(m,?1H,?ArH),?8.12-8.14?(m,?1H,?ArH),?8.23-8.25?(m,?1H,?ArH)。
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (3)
1. a synthetic method for the chlorinated aromatic hydrocarbons compounds that trichloroisocyanuric acid participates in, is characterized in that:
Under the condition that arene compounds exists at acetonitrile, take inorganic salt as catalyzer, the trichloroisocyanuric acid of take carries out chlorination as chlorinating agent, it is 70～90 ℃ that reaction process is controlled temperature, time 1～24h, is cooled to room temperature, solids removed by filtration after reaction finishes, with Rotary Evaporators, remove solvent acetonitrile, obtain chlorinated aromatic hydrocarbons compounds;
Described inorganic salt are iron(ic) chloride;
The consumption of above-mentioned arene compounds, trichloroisocyanuric acid and inorganic salt calculates in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: inorganic salt are 0.5～1.5:1:0.04～0.5;
Described arene compounds, its structural formula is as follows:
Wherein R is NO
2-.
2. the synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid as claimed in claim 1 participates in, the consumption that it is characterized in that arene compounds wherein used, trichloroisocyanuric acid and iron(ic) chloride calculates in molar ratio, i.e. arene compounds: trichloroisocyanuric acid: inorganic salt iron(ic) chloride is 1:1.2:0.5.
3. the synthetic method of the chlorinated aromatic hydrocarbons compounds that a kind of trichloroisocyanuric acid as claimed in claim 2 participates in, is characterized in that chlorination process control temp is 85 ℃.
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| CN107118090B (en) * | 2017-06-15 | 2020-11-27 | 浙江中山化工集团股份有限公司 | Method for preparing 1-chloro-1' -chloroacetyl cyclopropane by taking trichloroisocyanuric acid as chlorinating agent |
| CN107235976A (en) * | 2017-07-12 | 2017-10-10 | 海门华祥医药科技有限公司 | A kind of synthetic method of the azaindole of 3 chlorine 7 |
| CN108794421A (en) * | 2018-08-16 | 2018-11-13 | 陈万通 | The method for preparing 2- Lv benzoxazoles and 2,6- dichloro benzoxazoles from o-aminophenol as chlorinating agent using Solid triphosgene |
| CN112142620B (en) * | 2020-10-12 | 2023-03-31 | 江西省科学院应用化学研究所 | Synthetic method of 2-amino-3, 5-dichloro-N-methylbenzamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197056A (en) * | 1997-04-15 | 1998-10-28 | 罗姆和哈斯公司 | Chlorination of substituted alkenes using trichloroisocyanuric acid |
| US5981789A (en) * | 1998-12-30 | 1999-11-09 | Occidental Chemical Corporation | Preparation of nuclear chlorinated aromatic compounds |
-
2012
- 2012-10-22 CN CN201210401934.7A patent/CN102875271B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197056A (en) * | 1997-04-15 | 1998-10-28 | 罗姆和哈斯公司 | Chlorination of substituted alkenes using trichloroisocyanuric acid |
| US5981789A (en) * | 1998-12-30 | 1999-11-09 | Occidental Chemical Corporation | Preparation of nuclear chlorinated aromatic compounds |
Non-Patent Citations (19)
| Title |
|---|
| & * |
| Ã |
| Aacute * |
| Atilde * |
| a等.UMA METODOLOGIA SIMPLES E EFICIENTE PARA A CLORA& * |
| a等.UMA METODOLOGIA SIMPLES E EFICIENTE PARA A CLORAÇ |
| Ccedil * |
| Chlorination of Aromatic Systems with Trichloroisocyanuric Acid under Polar and Free-Radical Conditions;ERIC C. JUENGE等;《The Journal of Organic Chemistry》;19790331;第35卷(第3期);第719-772页 * |
| CIDO TRICLORO-ISOCIAN& * |
| CIDO TRICLORO-ISOCIANÚ |
| ERIC C. JUENGE等.Chlorination of Aromatic Systems with Trichloroisocyanuric Acid under Polar and Free-Radical Conditions.《The Journal of Organic Chemistry》.1979,第35卷(第3期),第719-772页. |
| Gabriela F. Mendon& * |
| Gabriela F. Mendonç |
| O DE COMPOSTOS AROMÁ |
| O DE COMPOSTOS AROM& * |
| RICO.《Quim. Nova》.2008,第31卷(第41期),第798-801页. * |
| TICOSATIVADOS UTILIZANDO O Á |
| TICOSATIVADOS UTILIZANDO O & * |
| Uacute * |
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