CN104086480A - Preparation method of 2-chloro-5-chloromethylpyridine - Google Patents
Preparation method of 2-chloro-5-chloromethylpyridine Download PDFInfo
- Publication number
- CN104086480A CN104086480A CN201410281195.1A CN201410281195A CN104086480A CN 104086480 A CN104086480 A CN 104086480A CN 201410281195 A CN201410281195 A CN 201410281195A CN 104086480 A CN104086480 A CN 104086480A
- Authority
- CN
- China
- Prior art keywords
- ccmp
- preparing
- grams
- cmp
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 5
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 229950009390 symclosene Drugs 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 230000000977 initiatory effect Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims description 16
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 2
- VXLYOURCUVQYLN-UHFFFAOYSA-N 2-chloro-5-methylpyridine Chemical compound CC1=CC=C(Cl)N=C1 VXLYOURCUVQYLN-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- IERHLVCPSMICTF-XVFCMESISA-N CMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C(=O)N=C(N)C=C1)O)O IERHLVCPSMICTF-XVFCMESISA-N 0.000 description 37
- 239000013317 conjugated microporous polymer Substances 0.000 description 37
- 210000003643 myeloid progenitor cell Anatomy 0.000 description 37
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000001131 transforming effect Effects 0.000 description 8
- 150000007973 cyanuric acids Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a fine chemical engineering intermediate, and particularly relates to a preparation method of 2-chloro-5-chloromethylpyridine. With 2-chloro-5-methyl pyridine (represented by the formula I) as a raw material, an initiation reaction is carried out with trichloroisocyanuric acid (represented by the formula III) through a chemical initiator or a light source under conditions of the temperature of 80-200 DEG C and an ordinary pressure or a micro negative pressure, after the reaction, 2-chloro-5-chloromethylpyridine is obtained through filtering, wherein the equation is described in the specification. Compared with a chlorine gas method with higher dangerousness, the method not only avoid the use of a solvent, but also omits neutralization, water washing and other processes in the traditional chlorination process, and avoids generation of waste water and acidic tail gas.
Description
Technical field
The present invention relates to the preparation method of fine-chemical intermediate, specifically a kind of method of preparing CCMP.
Background technology
CCMP (2-chloro-5-chloromethylpyridine, be called for short CCMP) be the shared key intermediate of the nicotinoids agricultural chemicals such as Provado, acetamiprid, Ti304, also be one of fine-chemical intermediate of current consumption maximum, the quality of its production technique is very remarkable to environmental influence.
At present the method for the synthetic CCMP that (is called for short direct chlorination method) taking CMP as raw material one one-step chlorination of report has chlorinated with chlorine method (US4778896, US Patent No. 5324841 and US5198549) and t-butyl hypochlorate chlorination process (Huaxue Shiji, Volume:20, Issue:5, Pages:313-316, Journal, 1998).But, chlorinated with chlorine method can inevitably generate the byproduct hydrogen chloride with the chlorine equimolar amount that consumes in reaction process, this hydrogenchloride is combined and is made system be strongly-acid with CMP and CCMP, the distillation operation that just can carry out after must fully neutralizing, shown in formula specific as follows:
Because the benzyl chloride activity of CCMP is higher, this system adopt in the highly basic such as sodium hydroxide and time can make product significantly decompose and reduce yield and the content of product.At present the better neutralization reagent of this system is generally the inorganic weak bases such as sodium bicarbonate that solubleness is lower, thus produce a large amount of in and waste water; In addition, in t-butyl hypochlorate chlorination process, the preparation of t-butyl hypochlorate has stricter regulation with preservation, and all has potential safety hazard in use and transportation, causes the method still in the laboratory study stage.
Summary of the invention
The object of the invention is to provide a kind of method of preparing CCMP.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method of preparing CCMP, taking CMP (formula I) as raw material, with trichloroisocyanuric acid (formula III) under 80～200 DEG C of normal pressures or micro-condition of negative pressure, carry out initiation reaction by chemical initiator or light source, after reaction, filtration obtains CCMP, and reaction formula is as follows:
After described initiation reaction, reaction solution is cooled to room temperature filtration, and filtrate is the crude mixture (also containing CMP and a small amount of chloro-5-dichloromethyl of 2-pyridine) of CCMP; Filter cake is callable cyanuric acid.
In reaction process, follow the tracks of terminal in feedstock conversion situation control reaction by gas-chromatography, generally choosing when CMP transformation efficiency reaches 50% left and right is the terminal of reaction, the consumption of the trichloroisocyanuric acid while reaching this reaction end is generally always feed intake the doubly left and right of 0.16-0.20 of molar weight of CMP, now CMP in the above-mentioned mixture leaching, CCMP, the content of the chloro-5-dichloromethyl of 2-pyridine is respectively 50%, 45% and 5% left and right, by rectifying, these three components are separated, wherein separate the chlorination reaction that can directly carry out next batch of the CMP obtaining.In the process of above-mentioned synthetic CCMP, do not produce hydrogenchloride, the by product cyanuric acid of recovery can again obtain TCCA (Trichloroisocyanuric acid) with chlorine reaction and be used, and is shown below:
Described initiation reaction temperature is 80～200 DEG C.
Described initiation reaction temperature is preferably 90～130 DEG C.
The add-on of described trichloroisocyanuric acid is 0.010-2.0 times of raw material CMP molar weight.
The add-on of described trichloroisocyanuric acid is preferably 0.15-0.5 times of raw material CMP molar weight.
The add-on of described initiator is 0.01-0.5 times of raw material CMP weight.
The add-on of described initiator is preferably 0.02-0.08 times of raw material CMP weight.
Described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or azo two isocapronitriles.
Described light source is the light source of wavelength 190-700nm.
The present invention has advantages of: the technology of synthetic CCMP provided by the invention, taking CMP as raw material, under condition of no solvent, taking TCCA (Trichloroisocyanuric acid) as chlorizating agent, causes one-step synthesis CCMP by initiator or illumination.And compared with traditional chlorinated with chlorine method, 1) the present invention, without using solvent to dilute in reaction process, can significantly increase production capacity, and can significantly reduce a large amount of energy consumptions that cause because of precipitation; 2) safer compared with chlorine when TCCA (Trichloroisocyanuric acid) is reinforced, convenient, be easy to metering, and system is neutral after reaction finishes, without neutralization, thereby avoided the generation of waste water, and the wastewater flow rate of 1 ton of CCMP of the every production of chlorinated with chlorine method reaches 4 tons of left and right.
Embodiment
Embodiment 1
The CMP of 38.5 grams of content 99.0% (0.3mol) is added in the chlorination reaction bottle with the 100ml of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, add 0.8 gram of Diisopropyl azodicarboxylate and 15.2 grams of TCCA (Trichloroisocyanuric acid) (0.06mol) that load weighted content is 92%.Reaction finishes rear system and is naturally down to room temperature, filters and reclaim 7.8 grams of cyanuric acids; Obtain 44.5 grams of filtrates, CCMP content is 43.8%, and the actual measurement pH value of filtrate is 6-7, and rectifying obtains 23.8 grams of CMPs, and content is 98.0%; Obtain 16.1 grams of CCMP, content is 97.0%, and in the CMP transforming, yield is 83.1%.
Embodiment 2
The CMP of 70.8 grams of content 99.0% (0.55mol) is added in the chlorination reaction bottle with the 100ml of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, add 5.6 grams of Diisopropyl azodicarboxylates and 32.4 grams of TCCA (Trichloroisocyanuric acid) (0.13mol) that load weighted content is 92%.Reaction finishes rear system and is naturally down to room temperature, filters and reclaim 18.5 grams of cyanuric acids; Obtain 84.5 grams of filtrates, CCMP content is 51.6%, and the actual measurement pH value of filtrate is 6-7, and rectifying obtains 31.7 grams of CMPs, and content is 99.0%; Obtain 42.3 grams of CCMP, content is 97.1%, and in the CMP transforming, yield is 83.5%.
Embodiment 3
The CMP of 127.5 grams of content 99.0% (1.0mol) is added in the chlorination reaction bottle with the 250ml of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, add 0.5 gram of Diisopropyl azodicarboxylate and 50.5 grams of TCCA (Trichloroisocyanuric acid) (0.20mol) that load weighted content is 92%.In the reinforced process of TCCA (Trichloroisocyanuric acid), visual response situation is added Diisopropyl azodicarboxylate, uses altogether 6.0 grams of Diisopropyl azodicarboxylates.Reaction finishes rear system and is naturally down to room temperature, 27.5 grams of filtered and recycled cyanuric acids; Obtain 150.0 grams of filtrates, CCMP content is 51.3%, and the actual measurement pH value of this filtrate is 6-7, and rectifying obtains 61.3 grams of CMPs, and content is 98.5%; Obtain CCMP73.0 gram, content is 97.5%, and in the CMP transforming, yield is 85.1%.
Embodiment 4
The CMP of 155.0 grams of content 99.0% (1.20mol) is joined in the chlorination reaction bottle with the 500ml of thermometer, condenser and drying tube, be warmed up to 90 DEG C-110 DEG C, add 0.5 gram of Diisopropyl azodicarboxylate and 63.3 grams of TCCA (Trichloroisocyanuric acid) (0.25mol) that load weighted content is 92%.In the reinforced process of TCCA (Trichloroisocyanuric acid), visual response situation is added Diisopropyl azodicarboxylate, uses altogether 7.2 grams of Diisopropyl azodicarboxylates.Reaction finishes rear system and is naturally down to room temperature, 31.5 grams of filtered and recycled cyanuric acids; Obtain 189.0 grams of filtrates, CCMP content is 54.2%, and the actual measurement pH value of this filtrate is 6-7, and rectifying obtains 65.1 grams of CMPs, and content is 98.0%; Obtain CCMP99.2 gram, content is 98.0%, and in the CMP transforming, yield is 85.3%.
Embodiment 5
The CMP of 38.5 grams of content 99.0% (0.3mol) is added in the chlorination reaction bottle with the 100ml of thermometer, condenser and drying tube, be warmed up to 120 DEG C-140 DEG C, add 1.2 grams of Diisopropyl azodicarboxylates and 25.3 grams of TCCA (Trichloroisocyanuric acid) (0.1mol) that load weighted content is 92%.Reaction finishes rear system and is naturally down to room temperature, filters and reclaim 13.8 grams of cyanuric acids; Obtain 49.5 grams of filtrates, CCMP content is 59.8%, and the actual measurement pH value of filtrate is 6-7, and rectifying obtains 11.2 grams of CMPs, and content is 98.0%; Obtain 25.1 grams of CCMP, content is 96.1%, and in the CMP transforming, yield is 70.1%.
Embodiment 6
The CMP of 38.5 grams of content 99.0% (0.3mol) is added in the chlorination reaction bottle with the 100ml of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, open ultraviolet lamp (220V, 250W, 190-300nm), 15.2 grams of TCCA (Trichloroisocyanuric acid) (0.06mol) that load weighted content is 92% are added in system and reacted.Reaction finishes rear system and is naturally down to room temperature, filters and reclaim 8.0 grams of cyanuric acids; Obtain 44.5 grams of filtrates, CCMP content is 43.6%, and the actual measurement pH value of filtrate is 6-7, and rectifying obtains 24.1 grams of CMPs, and content is 98.0%; Obtain 15.7 grams of CCMP, content is 98.0%, and in the CMP transforming, yield is 83.5%.
Embodiment 7
The CMP (0.3mol) that 38.9 grams (content 98.0%) is reclaimed adds in the chlorination reaction bottle with the 100ml of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, add 1.5 grams of Diisopropyl azodicarboxylates and 15.2 grams of TCCA (Trichloroisocyanuric acid) (0.06mol) that load weighted content is 92%.Reaction finishes rear system and is naturally down to room temperature, filters and reclaim 7.8 grams of cyanuric acids; Obtain 44.5 grams of filtrates, CCMP content is 43.8%, and the actual measurement pH value of filtrate is 6-7, and rectifying obtains 23.3 grams of CMPs, and content is 98.0%; Obtain 17.1 grams of CCMP, content is 97.5%, and in the CMP transforming, yield is 86.0%.
Comparative example
The CMP of 123.0 grams of content 99.0% (0.96mol) and 245 grams of chlorobenzenes are joined in the chlorination reaction bottle with the 1L of thermometer, condenser and drying tube, be warmed up to 100 DEG C-120 DEG C, add 1.0 grams of Diisopropyl azodicarboxylates and in 6 hours, pass into continuously 28 grams of dry chlorine gas (0.39mol).In logical chlorine process, visual response situation is added Diisopropyl azodicarboxylate, uses altogether 5.7 grams of Diisopropyl azodicarboxylates.Reaction finishes rear system and is naturally down to room temperature, slowly adds the saturated sodium bicarbonate solution of 380 grams to be stirred to without Bubble formation in phase system; Afterwards by mixed solution layering, organic phase and water two-phase.Organic phase is dry, obtain 135.8 grams, CCMP mixture after precipitation, and CCMP content is that 42.8%, pH value is 6-7, and rectifying obtains 77.9 grams of CMPs, and content is 98.0%; Obtain CCMP50.5 gram, content is 97.1%, and in the CMP transforming, yield is 85.0%.Above-mentioned water be in and waste water, weight is 377 grams, contain remaining chlorobenzene and neutralization generate sodium-chlor.
Claims (10)
1. prepare the method for CCMP for one kind, it is characterized in that: taking CMP as raw material, with trichloroisocyanuric acid under 80～200 DEG C of normal pressures or micro-condition of negative pressure, carry out initiation reaction by chemical initiator or light source, after reaction, filter and be CCMP; Reaction formula is as follows,
2. by the method for preparing CCMP claimed in claim 1, it is characterized in that:
After described initiation reaction, reaction solution is cooled to room temperature filtration, and filtrate is the crude mixture of CCMP, and rectifying obtains CCMP; Filter cake is the cyanuric acid reclaiming.
3. by the method for preparing CCMP claimed in claim 1, it is characterized in that:
Described initiation reaction temperature is 80～200 DEG C.
4. by the method for preparing CCMP claimed in claim 3, it is characterized in that:
Described initiation reaction temperature is 90～130 DEG C.
5. by the method for preparing CCMP claimed in claim 1, it is characterized in that:
The add-on of described trichloroisocyanuric acid is 0.010-2.0 times of raw material CMP molar weight.
6. by the method for preparing CCMP claimed in claim 5, it is characterized in that: the add-on of described trichloroisocyanuric acid is 0.15-0.5 times of raw material CMP molar weight.
7. by the method for preparing CCMP claimed in claim 1, it is characterized in that:
The add-on of described initiator is 0.01-0.5 times of raw material CMP weight.
8. by the method for preparing CCMP claimed in claim 7, it is characterized in that:
The add-on of described initiator is 0.02-0.08 times of raw material CMP weight.
9. by the method for preparing CCMP described in claim 1,7 or 8, it is characterized in that: described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or azo two isocapronitriles.
10. by the method for preparing CCMP claimed in claim 1, it is characterized in that:
Described light source is the light source of wavelength 190-700nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410281195.1A CN104086480A (en) | 2014-06-20 | 2014-06-20 | Preparation method of 2-chloro-5-chloromethylpyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410281195.1A CN104086480A (en) | 2014-06-20 | 2014-06-20 | Preparation method of 2-chloro-5-chloromethylpyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104086480A true CN104086480A (en) | 2014-10-08 |
Family
ID=51634271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410281195.1A Pending CN104086480A (en) | 2014-06-20 | 2014-06-20 | Preparation method of 2-chloro-5-chloromethylpyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086480A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844648A (en) * | 2015-04-02 | 2015-08-19 | 中国人民解放军63975部队 | Synthetic method of phosphorothioate compound |
| CN107162962A (en) * | 2017-05-12 | 2017-09-15 | 江苏克胜作物科技有限公司 | The control method of the PMC dimer of 2 chlorine 5 |
| CN107739331A (en) * | 2017-09-27 | 2018-02-27 | 九江善水科技股份有限公司 | A kind of synthetic method of the PMC of 2 chlorine 5 |
| WO2018183788A1 (en) | 2017-03-31 | 2018-10-04 | International Flavors & Fragrances Inc. | Chemical process of preparing dehydrohedione |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516848A (en) * | 2006-07-20 | 2009-08-26 | 拜尔农作物科学股份公司 | N'-cyano-N-alkyl halide imide amide derivatives |
| CN101906068A (en) * | 2009-06-04 | 2010-12-08 | 浙江医药股份有限公司新昌制药厂 | Preparation method of 2-pyridine carboxaldehyde |
| CN103274989A (en) * | 2013-06-08 | 2013-09-04 | 南京正荣医药化学有限公司 | Preparation method of octahydrocyclopenta[C]pyrrole derivatives and salts thereof |
| CN103787982A (en) * | 2012-10-31 | 2014-05-14 | 上海特化医药科技有限公司 | Telmisartan preparation method and intermediate of telmisartan |
-
2014
- 2014-06-20 CN CN201410281195.1A patent/CN104086480A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516848A (en) * | 2006-07-20 | 2009-08-26 | 拜尔农作物科学股份公司 | N'-cyano-N-alkyl halide imide amide derivatives |
| CN101906068A (en) * | 2009-06-04 | 2010-12-08 | 浙江医药股份有限公司新昌制药厂 | Preparation method of 2-pyridine carboxaldehyde |
| CN103787982A (en) * | 2012-10-31 | 2014-05-14 | 上海特化医药科技有限公司 | Telmisartan preparation method and intermediate of telmisartan |
| CN103274989A (en) * | 2013-06-08 | 2013-09-04 | 南京正荣医药化学有限公司 | Preparation method of octahydrocyclopenta[C]pyrrole derivatives and salts thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张品 等: "高效、低毒杀虫剂噻虫啉的合成工艺研究", 《精细化工中间体》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844648A (en) * | 2015-04-02 | 2015-08-19 | 中国人民解放军63975部队 | Synthetic method of phosphorothioate compound |
| WO2018183788A1 (en) | 2017-03-31 | 2018-10-04 | International Flavors & Fragrances Inc. | Chemical process of preparing dehydrohedione |
| US11198667B2 (en) | 2017-03-31 | 2021-12-14 | International Flavors & Fragrances Inc. | Chemical process of preparing dehydrohedione |
| CN107162962A (en) * | 2017-05-12 | 2017-09-15 | 江苏克胜作物科技有限公司 | The control method of the PMC dimer of 2 chlorine 5 |
| CN107739331A (en) * | 2017-09-27 | 2018-02-27 | 九江善水科技股份有限公司 | A kind of synthetic method of the PMC of 2 chlorine 5 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086480A (en) | Preparation method of 2-chloro-5-chloromethylpyridine | |
| CN103224451B (en) | Method for synthesizing 3,5-dichlorobenzoic acid | |
| CN104478793A (en) | Synthetic method of 2, 3, 5-trichloropyridine | |
| CN103641077B (en) | A kind of circulation utilization method of sodium hydrosulfite wastewater | |
| CN102229548A (en) | Method for producing thioglycollic acid | |
| CN107556214B (en) | A kind of preparation method of paracyanobenzoic acid | |
| CN102964270B (en) | Method for reducing hydrazine synthesized by diazonium salt by utilizing sodium sulphite | |
| CN104003888A (en) | Preparation method of 2,4-binitro-6-chloroaniline | |
| CN107522336A (en) | The processing method of caused acid waste water in a kind of contraposition ester production process | |
| CN103242190B (en) | Synthetic method of propyzamide | |
| CN104230703A (en) | Method for synthesizing high-purity benzoyl chloride | |
| CN104086400A (en) | Production process of sodium naphthalene acetate | |
| CN103880717B (en) | The preparation method of two (3-allyl group-4-hydroxy phenyl) sulfones and derivative thereof | |
| CN102659088A (en) | Water-phase synthesis method of sodium azide | |
| CN105367489A (en) | Method for synthesizing salazosulfapyridine using pyridazol as raw material | |
| CN105646397A (en) | Preparation method of flufenacet | |
| CN102849789A (en) | Preparation method for stannic chloride pentahydrate | |
| CN103319383B (en) | Preparation method of p-methylsulfonylbenzoic acid | |
| CN108640857B (en) | Synthesis process of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylamidine | |
| TWI735573B (en) | Methods of manufacturing certain substituted sulfilimines | |
| CN103641797B (en) | Preparation method for N-acetyl morpholine | |
| CN105085381B (en) | A kind of separation method of chloro-pyridine mixture | |
| CN110818557A (en) | Synthesis method of o-chloromethyl benzoyl chloride | |
| CN104311466A (en) | Synthetic method of improved sodium 2,3-dimercaptosulphonate | |
| CN101597265B (en) | Method for synthesizing bromacil technical |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160114 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Applicant after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 110021 Liaodong, Liaoning, Tiexi Shen road, No. 8, No. Applicant before: Shenyang Research Institute of Chemical Industry |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141008 |