CN108373434A - A method of nitre phenylate is synthesized by 2- amino -5- nitrotoleunes - Google Patents
A method of nitre phenylate is synthesized by 2- amino -5- nitrotoleunes Download PDFInfo
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- CN108373434A CN108373434A CN201810295563.6A CN201810295563A CN108373434A CN 108373434 A CN108373434 A CN 108373434A CN 201810295563 A CN201810295563 A CN 201810295563A CN 108373434 A CN108373434 A CN 108373434A
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- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 10
- WCMLRSZJUIKVCW-UHFFFAOYSA-N 4-(trifluoromethyl)benzenethiol Chemical compound FC(F)(F)C1=CC=C(S)C=C1 WCMLRSZJUIKVCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 8
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000001119 stannous chloride Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001256 steam distillation Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 abstract 2
- 229910052801 chlorine Inorganic materials 0.000 abstract 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- OCINXEZVIIVXFU-UHFFFAOYSA-N 1-methyl-3-[3-methyl-4-[4-(trifluoromethylthio)phenoxy]phenyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(SC(F)(F)F)C=C1 OCINXEZVIIVXFU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229960000898 toltrazuril Drugs 0.000 description 4
- 241000224483 Coccidia Species 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002829 nitrogen Chemical class 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical class O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003224 coccidiostatic agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical group [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000003660 reticulum Anatomy 0.000 description 1
- 210000001563 schizont Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of medicine synthesis, relate in particular to a kind of method that nitre phenylate is synthesized by 2 amino, 5 nitrotoleune, it is reacted with hydrochloric acid, sodium nitrite with 2 amino, 5 nitrotoleune and generates diazol, diazol is reacted with hydrochloric acid, stannous chloride generates 2 chlorine, 5 nitrotoleune；Again using 4 trifluoromethylthio phenol and 2 chlorine, 5 nitrotoleune as raw material, using potassium carbonate as acid binding agent, using dimethyl sulfoxide as solvent, using toluene as deicer, back flow reaction obtains nitre phenylate.The present invention uses back flow reaction under the reaction temperature higher than toluene water azeotropic temperature, utilizes toluene and water azeotropic principles so that moisture is free in except reaction system, to which driving a reaction carries out；Reaction yield is substantially increased, and product can put into without purifying and react in next step.
Description
Technical field
The present invention relates to technical field of medicine synthesis, relate in particular to a kind of by the synthesis of 2- amino -5- nitrotoleunes
The method of nitre phenylate.
Background technology
Toltrazuril category triazineon compounds have wide spectrum coccidiostat activity, are widely used in chicken coccidiasis.Toltrazuril pair
The site of action of coccidia is very extensive, has effect to two asexual cycles of coccidia, such as inhibits schizont, the core of microgametophyte
The wall of division and microgametophyte forms body.Since this product interferes coccidia nuclear division and mitochondria, influence polypide breathing and
Metabolic function can be such that endocytoplasmic reticulum expands again in addition, and serious ghost occurs, thus with worm effect of killing.
On domestic market, toltrazuril has been realized in production domesticization, but is limited to process conditions and cost of material, production
Product price costly, therefore improves technique, and New Research Method becomes the research hotspot of such veterinary drug worker.
3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitrobenzene is the important intermediate of synthesis toltrazuril, but to it
Study of synthesis method, the technique study for being especially suitable for industrialization large-scale production are still insufficient.
Invention content
Pass through 2- amino -5- nitro first the purpose of the present invention is to provide a kind of high yield, suitable for industrialized production
The method that benzene synthesizes nitre phenylate.
To solve the above problems, the technical solution adopted by the present invention is as follows：One kind is synthesized by 2- amino -5- nitrotoleunes
The method of nitre phenylate：
(1) 2- amino -5- nitrotoleunes are reacted with hydrochloric acid, sodium nitrite generates diazol；
(2) it takes hydrochloric acid, stannous chloride to be added in reaction vessel, 20 DEG C or less is cooled to after stirring lower dissolving；Step is added
(1) diazol obtained；Keep after reaction temperature reacts 1~3h at 20 DEG C or less, be warming up to 50~60 DEG C of insulation reactions 1~
3h；Steam distillation obtains the chloro- 5- nitrotoleunes of 2- after reaction；
(3) using 4- trifluoromethylthios phenol and the chloro- 5- nitrotoleunes of 2- as raw material, using potassium carbonate as acid binding agent, with diformazan
Sulfoxide is solvent, flows back using toluene as deicer, at 120~140 DEG C and 3- methyl -4- (4- trifluoromethylthios benzene) oxygen is obtained by the reaction
Base nitrobenzene；The dosage of the solvent dimethyl sulfoxide can dissolve raw material just at the reaction temperatures and be preferred；Specifically, described molten
The dosage of agent dimethyl sulfoxide is 0.5~2 kilogram/every mole 4- trifluoromethylthio phenol；Further, the solvent dimethyl sulfoxide
Dosage be 0.6~1 kilogram/every mole 4- trifluoromethylthio phenol.
Preferably, specific operation is as follows in the step (1)：2- amino -5- nitrotoleunes are dissolved in 2~4 times of quality
The concentrated sulfuric acid after, be added dropwise 1~3 times of quality water, warm naturally to be cooled to 0 DEG C after 2- amino -5- nitrotoleunes are completely dissolved
Hereinafter, the technical hydrochloric acid (30% mass concentration) of 1~3 times of quality is added, 25% sodium nitrite solution is added dropwise.Above-mentioned 2~4 times, 1
~3 times using the quality of 2- amino -5- nitrotoleunes as comparison other.
Preferably, the additive amount of sodium nitrite described in the step (1) is the 1 of 2- amino -5- nitrotoleune moles
~1.1 times.
Preferably, hydrochloric acid addition is 3~6 times of 2- amino -5- nitrotoleune quality in the step (2)；The step
Suddenly stannous chloride addition is 1~1.5 times of 2- amino -5- nitrotoleune quality in (2).
Preferably, the 4- trifluoromethylthios phenol and the chloro- 5- nitrotoleunes molar ratios of 2- are 1：1.
Preferably, the reaction temperature is 130 DEG C.
Preferably, the volume ratio of the dimethyl sulfoxide and toluene is 2~6：1.Further, the dimethyl sulfoxide and toluene
Volume ratio be 2~5：1.
Preferably, the mole dosage of the potassium carbonate is the 0.6~0.8 of 4- trifluoromethylthio phenol moles.
Preferably, the reaction time is 3~5 hours, and solvent is evaporated under reduced pressure out in 90~110 DEG C after the completion of reaction, and
Add water and toluene to be washed, extracted, toluene phase is collected after extraction, can direct plunge into and react in next step.
Preferably, the toluene dosage for washing, extracting is product 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitro
2~5 times of benzene quality；The further toluene dosage for washing, extracting is product 3- methyl -4- (4- trifluoromethylthios benzene)
2~2.5 times of oxygroup nitrobenzene quality.
Preferably, the water consumption for washing, extracting is 0.9~2 times of toluene quality.
It is generally acknowledged that being reacted as follows by the generation of acid binding agent of potassium carbonate：
a.K2CO3+HCl→KHCO3+KCl
If it is, then the input amount of potassium carbonate should reach at least hydrogen chloride mole can just play it is good
" tiing up acid " acts on, and the mole of potassium carbonate only has 0.6~0.8 in the present invention；Actually when reaction temperature reach 100 DEG C with
On, saleratus can occur to react as follows：
b.2KHCO3→K2CO3+CO2+H2O
The equation of two-step reaction merge just at：
c.K2CO3+2HCl→2KCl+CO2+H2O
Usual etherification reaction avoids water, is that not will produce water method by reaction equation a, but at a temperature of this reaction, carbon
The decomposition of potassium hydrogen phthalate is also inevitable.Therefore, a reaction that will not conventionally generate water is given birth to due to reaction temperature
At water, but due to the low boiling point of raw material, and the conventional mode that vacuumizes can not be used to remove water, cause reaction yield that can not obtain
It breaks through.
In the application as chemical name conflicts with structural formula, it is subject to structural formula.
The advantageous effect of technical solution using the present invention is：Using under the reaction temperature higher than toluene-water azeotropic temperature
Back flow reaction utilizes toluene and water azeotropic principles so that moisture is free in except reaction system, to which driving a reaction carries out；Both
Avoid traditional loss for vacuumizing 4- trifluoromethylthios phenol under mode, the product for high yield of getting back, by reaction yield
97~98% are increased to from 85% or so of existing method, and product can put into without purifying and react in next step, it is significantly simple
Change reaction condition, reduces production cost.
Specific implementation mode
The present invention is further described specifically with reference to embodiments, but not limited to this.
Embodiment 1
2- amino -5- nitrotoleune 152kg are taken, are dissolved in the concentrated sulfuric acid of 450kg, 300kg water is added dropwise, warms naturally to
100 DEG C, after 2- amino -5- nitrotoleunes all dissolving, it is cooled to 0 DEG C, the technical hydrochloric acid that mass concentration is 30% is added
300kg keeps reacting liquid temperature to be no more than 0 DEG C in adition process, 25% sodium nitrite solution 276kg is at the uniform velocity added, and obtains weight
Nitrogen salt solution；
600kg technical hydrochloric acids, the lower dissolving of 195kg stannous chlorides stirring are added into another reaction kettle, temperature drops after dissolving
To 20 DEG C hereinafter, by diazonium salt solution be rapidly added in the reaction kettle quickly stirring hydrolyze, heat preservation 2 hours after be warming up to 55 DEG C after
Continuation of insurance temperature 2 hours.Heating, steam distillation go out the chloro- 5- nitrotoleunes 158kg of 2-, yield 92%.
Take 4- trifluoromethylthio phenol 200kg, 2- chloro- 5- nitrotoleunes 175kg, potassium carbonate 95kg, dimethyl sulfoxide
600kg, toluene 115kg are added in reaction kettle；Controlled at carrying out back flow reaction within the scope of 120~130 DEG C；React 5h after in
90~110 DEG C are evaporated under reduced pressure out solvent, and 1600kg water and 800kg toluene are added to be washed, extracted, and toluene is collected after extraction
Phase removes solvent and obtains 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitrobenzene 326kg, purity 99%, yield 97.1%.
Embodiment 2
2- amino -5- nitrotoleune 152kg are taken, are dissolved in the concentrated sulfuric acid of 600kg, 150kg water is added dropwise, warms naturally to
100 DEG C, after 2- amino -5- nitrotoleunes all dissolving, it is cooled to 0 DEG C, the technical hydrochloric acid that mass concentration is 30% is added
300kg keeps reacting liquid temperature to be no more than 0 DEG C in adition process, 25% sodium nitrite solution 276kg is at the uniform velocity added, and obtains weight
Nitrogen salt solution；
450kg technical hydrochloric acids, the lower dissolving of 225kg stannous chlorides stirring are added into another reaction kettle, temperature drops after dissolving
To 20 DEG C hereinafter, by diazonium salt solution be rapidly added in the reaction kettle quickly stirring hydrolyze, heat preservation 2 hours after be warming up to 55 DEG C after
Continuation of insurance temperature 2 hours.Heating, steam distillation go out the chloro- 5- nitrotoleunes 160kg of 2-, yield 93.3%.
Take 4- trifluoromethylthio phenol 200kg, 2- chloro- 5- nitrotoleunes 175kg, potassium carbonate 93.5kg, dimethyl sulfoxide
700kg, toluene 150kg are added in reaction kettle；Controlled at carrying out back flow reaction within the scope of 130~140 DEG C；React 3h after in
100~110 DEG C are evaporated under reduced pressure out solvent, and 600kg water and 650kg toluene are added to be washed, extracted, and toluene is collected after extraction
Phase removes solvent and obtains 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitrobenzene 325kg, purity 99%, yield 96.8%.
Embodiment 3
2- amino -5- nitrotoleune 152kg are taken, are dissolved in the concentrated sulfuric acid of 300kg, 450kg water is added dropwise, warms naturally to
100 DEG C, after 2- amino -5- nitrotoleunes all dissolving, it is cooled to 0 DEG C, the technical hydrochloric acid that mass concentration is 30% is added
300kg keeps reacting liquid temperature to be no more than 0 DEG C in adition process, 25% sodium nitrite solution 276kg is at the uniform velocity added, and obtains weight
Nitrogen salt solution；
900kg technical hydrochloric acids, the lower dissolving of 150kg stannous chlorides stirring are added into another reaction kettle, temperature drops after dissolving
To 20 DEG C hereinafter, by diazonium salt solution be rapidly added in the reaction kettle quickly stirring hydrolyze, heat preservation 2 hours after be warming up to 55 DEG C after
Continuation of insurance temperature 2 hours.Heating, steam distillation go out the chloro- 5- nitrotoleunes 155kg of 2-, yield 90.4%.
Take 4- trifluoromethylthio phenol 200kg, 2- chloro- 5- nitrotoleunes 172kg, potassium carbonate 96.6kg, dimethyl sulfoxide
1000kg, toluene 160kg are added in reaction kettle；Controlled at carrying out back flow reaction within the scope of 125~135 DEG C；After reacting 4h
It is evaporated under reduced pressure out solvent in 100~110 DEG C, and 600kg water and 650kg toluene is added to be washed, extracted, toluene is collected after extraction
Phase removes solvent and obtains 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitrobenzene 326kg, purity 99%, yield 97.1%.
All documents that the present invention refers to are incorporated herein by reference, and are individually drawn just as each document
It is used as with reference to such.
Claims (10)
1. a kind of method synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, includes the following steps：
(1) 2- amino -5- nitrotoleunes are reacted with hydrochloric acid, sodium nitrite generates diazol；
(2) it takes hydrochloric acid, stannous chloride to be added in reaction vessel, 20 DEG C or less is cooled to after stirring lower dissolving；Step (1) is added to obtain
The diazol arrived；After keeping reaction temperature to react 1~3h at 20 DEG C or less, it is warming up to 50~60 DEG C of 1~3h of insulation reaction；Reaction
After steam distillation obtain the chloro- 5- nitrotoleunes of 2-；
(3) using 4- trifluoromethylthios phenol and the chloro- 5- nitrotoleunes of 2- as raw material, using potassium carbonate as acid binding agent, with dimethyl sulfoxide
For solvent, flows back using toluene as deicer, at 120~140 DEG C and 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitre is obtained by the reaction
Base benzene；The 4- trifluoromethylthios phenol and the chloro- 5- nitrotoleunes molar ratios of 2- are 1：1.
2. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, which is characterized in that institute
It is as follows to state specific operation in step (1)：After 2- amino -5- nitrotoleunes are dissolved in the concentrated sulfuric acid of 2~4 times of quality, dropwise addition 1~
The water of 3 times of quality warms naturally to be cooled to 0 DEG C after 2- amino -5- nitrotoleunes are completely dissolved hereinafter, 1~3 times of quality is added
Technical hydrochloric acid (30% mass concentration), be added dropwise 25% sodium nitrite solution.
3. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, which is characterized in that institute
The additive amount for stating sodium nitrite described in step (1) is 1~1.1 times of 2- amino -5- nitrotoleune moles.
4. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, which is characterized in that institute
State 3~6 times that hydrochloric acid addition in step (2) is 2- amino -5- nitrotoleune quality；Stannous chloride adds in the step (2)
Enter 1~1.5 times that amount is 2- amino -5- nitrotoleune quality.
5. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, it is characterised in that described
The volume ratio of dimethyl sulfoxide and toluene is 2~5：1.
6. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, it is characterised in that described
The mole dosage of potassium carbonate is the 0.6~0.8 of 4- trifluoromethylthio phenol moles.
7. special according to the method that claim 1~6 any one of them synthesizes nitre phenylate by 2- amino -5- nitrotoleunes
Sign is that the reaction time is 3~5 hours, is evaporated under reduced pressure out solvent after the completion of reaction in 90~110 DEG C, and add water and toluene
It washed, extracted, toluene phase is collected after extraction, can direct plungeed into and react in next step.
8. the method according to claim 7 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, it is characterised in that be used for
Washing, 2.5~5 times that the toluene dosage extracted is product 3- methyl -4- (4- trifluoromethylthios benzene) oxygroup nitrobenzene quality.
9. the method according to claim 7 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, it is characterised in that be used for
The dosage of the water of washing, extraction is 0.9~2 times of toluene quality.
10. the method according to claim 1 for synthesizing nitre phenylate by 2- amino -5- nitrotoleunes, it is characterised in that institute
The dosage for stating solvent dimethyl sulfoxide is 0.5~2 kilogram/every mole 4- trifluoromethylthio phenol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265351A (en) * | 2018-11-14 | 2019-01-25 | 沈阳化工研究院有限公司 | A kind of preparation method of the chloro- 5- nitro-toluene of 2- |
Citations (1)
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| CN101108831A (en) * | 2006-07-18 | 2008-01-23 | 洛阳普莱柯生物工程有限公司 | Method of producing toltrazuril |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265351A (en) * | 2018-11-14 | 2019-01-25 | 沈阳化工研究院有限公司 | A kind of preparation method of the chloro- 5- nitro-toluene of 2- |
| CN109265351B (en) * | 2018-11-14 | 2021-10-01 | 沈阳化工研究院有限公司 | Preparation method of 2-chloro-5-nitro-toluene |
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