CN1235874C - Chemical synthesis method of aryl isocyanate - Google Patents
Chemical synthesis method of aryl isocyanate Download PDFInfo
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- CN1235874C CN1235874C CN 02130077 CN02130077A CN1235874C CN 1235874 C CN1235874 C CN 1235874C CN 02130077 CN02130077 CN 02130077 CN 02130077 A CN02130077 A CN 02130077A CN 1235874 C CN1235874 C CN 1235874C
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- CN
- China
- Prior art keywords
- arylamine
- reaction
- aryl isocyanate
- trichloromethyl
- yield
- Prior art date
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- Expired - Fee Related
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- -1 aryl isocyanate Chemical class 0.000 title claims abstract description 12
- 239000012948 isocyanate Substances 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 abstract 2
- 239000002912 waste gas Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 1
- WKURVXXDGMYSDP-UHFFFAOYSA-N 2-propyl-aniline Chemical compound CCCC1=CC=CC=C1N WKURVXXDGMYSDP-UHFFFAOYSA-N 0.000 description 1
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Aryl isocyanate is an important intermediate product for organic synthesis. In the present invention, aryl isocyanate is prepared by the catalytic reaction between bis(trichloromethyl) carbonate and arylamine in organic solvent, wherein the bis(trichloromethyl) carbonate and the arylamine are used as raw materials. In the chemical synthesis method of the present invention, potential safety hazard, waste gas sources, waste liquid sources and waste residue sources are fundamentally eliminated. Thus, the method for preparing aryl isocyanate serial products has the advantages of easy raw material obtainment, safe and reliable preparation, high reaction yield, low preparation cost, basically no waste gas, waste liquid and waste residue.
Description
Technical field
The present invention relates to two (trichloromethyl) carbonic ethers of a kind of usefulness substitute phosgene or trichloromethylchloroformate directly and arylamine reaction prepare the chemical synthesis process of aryl isocyanate.Aryl isocyanate is mainly used in synthetic medicine, agricultural chemicals and macromolecular material.
Background technology
Before the present invention made, the existing main method of chemosynthesis aryl isocyanate was to be that raw material is synthesized into by arylamine photoreactive gas or trichloromethylchloroformate, for example UPS5556971, UPS3917847, UPS3763232, BP737487, FP1098303, day disclosure special permission 8052 (1983), EP147211 etc.Because phosgene (COCl
2) be the hypertoxic gas of the use of strict in the world control and limit production, no matter be laboratory work or industrial production, all there is very big potential safety hazard.Trichloromethylchloroformate is a liquid, and its security is big than phosgene, resolves into phosgene but run into gac, iron or organic amine etc., and storage and transportation etc. are also difficult, thereby still there is bigger potential safety hazard in use.
Summary of the invention
Task of the present invention is the shortcoming that overcomes prior art, provides one technology is reasonable, production safety is reliable, reaction yield is high, production cost is low, do not have substantially the aryl isocyanate series product chemical synthesis process of the three wastes.
The chemical synthesis process of aryl isocyanate, it is characterized in that with arylamine and two (trichloromethyl) carbonic ethers be raw material under the effect of catalyzer tetrabutyl urea, one of them is synthesized into as solvent to select benzene, toluene, chlorobenzene, dimethylbenzene, tetrahydrofuran (THF), tetracol phenixin and ethyl acetate; Perhaps selecting with benzene is solvent, and catalyzer is selected triethylamine, pyridine, N-methylpyrrole, and one of them is synthesized into; The molar ratio of above-mentioned reaction is an arylamine: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34～0.8: 0.001～0.1, and solvent load is 2-8 a times of arylamine quality, and its reaction equation is:
X
1，X
2，X
3＝H，CH
3，CH
2CH
3，CH
2CH
2CH
3，CH(CH
3)
2，F，Cl，Br，I
The present invention compared with prior art, the operational path advanced person, processing condition are reasonable, and used raw material is cheap and easy to get, avoided hypertoxic phosgene and trichloromethylchloroformate, safety simple to operate, the reaction yield height, generally more than 80%, production cost is low, substantially do not have the three wastes, have bigger implementary value and economic results in society.
Embodiment
Embodiment 1
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 100g, 250ml benzene and 3g tetrabutyl urea.Open and stir, and begin to drip 93g (1mol) aniline.Finish, be warming up to 70 ℃, and react 3h down at 70-80 ℃, reaction finishes the back underpressure distillation and reclaims benzene, collects cut-product phenylcarbimide 101g of 161-163 ℃ at last, and yield is 85%.Through the gas Chromatographic Determination product purity is 99.0%.
Embodiment 2
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.5: 0.01, and other is operated with example 1.Yield is 88%, and the phenylcarbimide product purity is more than 99.1%.
Embodiment 3
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether is 1: 0.75, and other is operated with example 1.Yield is 90%, and the phenylcarbimide product purity is 99.3%.
Embodiment 4
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.35: 0.001, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is 99.2%.
Embodiment 5
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.35: 0.001, and other is operated with example 1.Yield is 87%, and the phenylcarbimide product purity is 99.1%.
Embodiment 6
The volume ratio that feeds intake is an organic solvent: aniline is 5: 1, and other is operated with example 1.Yield is 85%, and the phenylcarbimide product purity is 99.5%.
Embodiment 7
Catalyzer changes triethylamine into, and other is operated with example 1.Yield is 80%, and the phenylcarbimide product purity is more than 98.2%.
Embodiment 8
Catalyzer changes pyridine into, and other is operated with example 1.Yield is 81%, and the phenylcarbimide product purity is more than 98.0%.
Embodiment 9
Catalyzer changes the N-methylpyrrole into, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is 99.0%.
Embodiment 10
Organic solvent changes toluene into, and temperature of reaction is upgraded to 100-110 ℃, and other is operated with example 1.Yield is 85%, and the phenylcarbimide product purity is more than 99%.
Embodiment 11
Organic solvent changes chlorobenzene into, and temperature of reaction is upgraded to 120-130 ℃, and other is operated with example 1.Yield is 84%, and the phenylcarbimide product purity is more than 99%.
Embodiment 12
Organic solvent changes dimethylbenzene into, and temperature of reaction is upgraded to 135-145 ℃, and other is operated with example 1.Yield is 82%, and the phenylcarbimide product purity is more than 99%.
Embodiment 13
Organic solvent changes tetrahydrofuran (THF) into, and temperature of reaction is upgraded to 60-67 ℃, and other is operated with example 1.Yield is 79%, and the phenylcarbimide product purity is more than 98%.
Embodiment 14
Organic solvent changes tetracol phenixin into, and temperature of reaction is upgraded to 70-80 ℃, and other is operated with example 1.Yield is 75%, and the phenylcarbimide product purity is more than 98%.
Embodiment 15
Organic solvent changes ethyl acetate into, and temperature of reaction is upgraded to 70-80 ℃, and other is operated with example 1.Yield is 80%, and the phenylcarbimide product purity is more than 98%.
Embodiment 16
Reaction times changes 5h into, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is more than 99%.
Embodiment 17
Reaction times changes 8h into, and other is operated with example 1.Yield is 84%, and the phenylcarbimide product purity is more than 99%.
Embodiment 18
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 110g, 250ml toluene and 3g tetrabutyl urea.Open and stir, and begin to drip 107g (1mol) para-totuidine.Finish, be warming up to 100 ℃, and at 100-110 ℃ of following reaction 3h, reaction finishes the back underpressure distillation and reclaims toluene, collect under the 1333pa cut-product phenylcarbimide 120g of 71-73 ℃ at last, yield is 90%.Through the gas Chromatographic Determination product purity is 99.0%.
Embodiment 19-28
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 110g, 250ml toluene and 3g tetrabutyl urea.Open and stir, and begin to drip the 1mol arylamine, about 0.5-1h.Finish, be warming up to backflow, and under relevant temperature, (see Table 1) reaction 1-10h, reaction finishes the back vacuum distillation recovered solvent, press the vacuum tightness underpressure distillation or the air distillation of table 1 at last and collect the cut of relevant temperature, get the product phenylcarbimide, yield and purity see Table 1.
Table 1
| Example 19-29 experimental result | ||||||
| Raw material-amine | Reaction times (h) | Solvent | Temperature of reaction (℃) | Vacuum tightness (Pa) | Collection cut temperature (℃) | Yield (%) |
| Ortho Toluidine | 2 | Toluene | 100-110 | Normal pressure | 184-186 | 88.5 |
| Meta-aminotoluene | 2 | Toluene | 100-110 | 1600 | 74-76 | 89 |
| O ethyl aniline | 2 | Toluene | 100-110 | 399.9 | 54-56 | 86.6 |
| 2-n-propyl aniline | 1.5 | Toluene | 100-110 | 6.7 | 49-51 | 82.5 |
| 4-tertiary butyl aniline | 1.5 | Toluene | 100-110 | 266.6 | 49-51 | 88.8 |
| Ortho-Chloro aniline | 3 | Chlorobenzene | 120-130 | 1333 | 82-84 | 90.1 |
| M-chloro aniline | 3 | Chlorobenzene | 120-130 | 1333 | 76-78 | 87.9 |
| P-Chlorobenzoic acid amide | 3 | Chlorobenzene | 120-130 | Normal pressure | 202-204 | 90.5 |
| O-bromoaniline | 3.5 | Chlorobenzene | 120-130 | 66.7 | 62-64 | 85.1 |
| M-bromoaniline | 3.5 | Chlorobenzene | 120-130 | Normal pressure | 219-221 | 85 |
| Para-bromoaniline | 3.5 | Chlorobenzene | 120-130 | 1866.2 | 157-159 | 88 |
The present invention and existing chemical synthesis process relatively have safety simple to operate, and reaction time is short, and reaction yield is high, good product quality, and the advantages such as non-environmental-pollution are methods that is suitable for suitability for industrialized production.
Claims (1)
1. the chemical synthesis process of aryl isocyanate, it is characterized in that with arylamine and two (trichloromethyl) carbonic ethers be raw material under the effect of catalyzer tetrabutyl urea, one of them is synthesized into as solvent to select benzene, toluene, chlorobenzene, dimethylbenzene, tetrahydrofuran (THF), tetracol phenixin and ethyl acetate; Perhaps selecting with benzene is solvent, and catalyzer is selected triethylamine, pyridine, N-methylpyrrole, and one of them is synthesized into; The molar ratio of above-mentioned reaction is an arylamine: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34～0.8: 0.001-0.1; Its solvent load is 2-8 a times of arylamine quality; Its temperature of reaction is 15-150 ℃, and its reaction times is 1～10h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130077 CN1235874C (en) | 2002-08-13 | 2002-08-13 | Chemical synthesis method of aryl isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130077 CN1235874C (en) | 2002-08-13 | 2002-08-13 | Chemical synthesis method of aryl isocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1475480A CN1475480A (en) | 2004-02-18 |
| CN1235874C true CN1235874C (en) | 2006-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02130077 Expired - Fee Related CN1235874C (en) | 2002-08-13 | 2002-08-13 | Chemical synthesis method of aryl isocyanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1235874C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939899B (en) * | 2005-09-26 | 2011-12-21 | 杭州崇舜化学有限公司 | Synthesis of 1,5-naphthalene isocyanate |
| CN104418773A (en) * | 2013-09-02 | 2015-03-18 | 上海龙翔生物医药开发有限公司 | Synthetic method of 2,4,5-trifluoro-benzene isocyanate and intermediate thereof |
| CN104447412A (en) * | 2014-11-12 | 2015-03-25 | 上海朗亿新材料科技有限公司 | Preparation method of isocyanate |
| CN104744306A (en) * | 2015-04-10 | 2015-07-01 | 湖南利洁生物化工有限公司 | P-chloroaniline isocyanate preparation method |
| CN110903216A (en) * | 2019-12-19 | 2020-03-24 | 山东华阳农药化工集团有限公司 | Preparation of diphenyl ethane diisocyanate by solid phosgene method and application thereof |
| CN112679388A (en) * | 2020-12-28 | 2021-04-20 | 浙江丽水有邦新材料有限公司 | Preparation method and preparation device of 2, 6-diisopropylbenzene isocyanate |
| CN113773230A (en) * | 2021-09-07 | 2021-12-10 | 京博农化科技有限公司 | Method for synthesizing diflubenzuron by one-pot method |
| CN114230489A (en) * | 2021-12-31 | 2022-03-25 | 浙江丽水有邦新材料有限公司 | Preparation and purification method and purification device of m-tolyl isocyanate |
-
2002
- 2002-08-13 CN CN 02130077 patent/CN1235874C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1475480A (en) | 2004-02-18 |
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