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Chemical Structure| 69045-83-6 Chemical Structure| 69045-83-6

Structure of 69045-83-6

Chemical Structure| 69045-83-6

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CAS No.: 69045-83-6

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Product Details of [ 69045-83-6 ]

CAS No. :69045-83-6
Formula : C6H2Cl5N
M.W : 265.35
SMILES Code : ClC1=CC(=CN=C1Cl)C(Cl)(Cl)Cl
MDL No. :MFCD03701543
InChI Key :XVBWGQSXLITICX-UHFFFAOYSA-N
Pubchem ID :94647

Safety of [ 69045-83-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 69045-83-6 ] Show Less

Physicochemical Properties

Num. heavy atoms 12
Num. arom. heavy atoms 6
Fraction Csp3 0.17
Num. rotatable bonds 1
Num. H-bond acceptors 1.0
Num. H-bond donors 0.0
Molar Refractivity 53.49
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

12.89 ?2

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

2.31
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

4.06
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

4.11
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

3.19
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

4.34
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

3.6

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-4.35
Solubility 0.0119 mg/ml ; 0.000045 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-4.03
Solubility 0.0245 mg/ml ; 0.0000923 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-5.16
Solubility 0.00186 mg/ml ; 0.000007 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

 High
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

 Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

 No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

 Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

 No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

 Yes
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

 No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

 No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-5.04 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

 0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

 None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

 0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

 0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

 1.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

2.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

 No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

 1.89

Application In Synthesis of [ 69045-83-6 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 69045-83-6 ]

[ 69045-83-6 ] Synthesis Path-Downstream   1~32

  • 1
  • [ 65550-81-4 ]
  • [ 69045-83-6 ]
  • 2
  • [ 69045-83-6 ]
  • [ 69045-84-7 ]
YieldReaction ConditionsOperation in experiment
92% With hydrogen fluoride; tungsten(VI) chloride; at 170 - 180℃; under 1500.15 Torr; for 5h;Autoclave; 26.5 g 0.1 mol <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong>,0.2 g of tungsten hexachlor into the reactor,Heated to 170 C at atmospheric pressure,And then hydrogen fluoride (about 20 g)The reaction is terminated when the test product is no longer changed,Unreacted hydrogen fluoride,After condensing recovery,The generated hydrogen chloride can be absorbed and removed.The reaction solution was cooled to room temperature,Transferred to an autoclave,Heated to 180 C,Pressure 0.2MPa,Reaction 5h,Cooling down,Sampling analysis,Containing 2,3-dichloro-5-trifluoromethylpyridine 94%Yield 92%.
73% With pyridine; iron(III) chloride; hydrogen fluoride; at 130 - 175℃;Autoclave; EXAMPLE 3 Conversion of <strong>[69045-83-6]2,3-dichloro-5-(trichloromethyl)pyridine</strong> to 2,3-dichloro-5- (trifluoromethyl)pyridine. <strong>[69045-83-6]2,3-dichloro-5-(trichloromethyl)pyridine</strong> (5 g, 18.84 mmole), iron(III) chloride (0.153 g, 0.942 mmole) and hydrogen fluoride (2.423 g, 85 mmole) in pyridine solution (70%) was added to an autoclave and heated to 175 C over night. The autoclave was cooled to 130 C and left for stirring additional 5 hours, followed by cooling to 25 C and opened carefully leaving gas phase through a Caustic Lye scrubber. The crude was dissolved in dichloromethane, washed with 1 M NaOH (aq) and water. The organic phase was removed by distillation and the product was obtained by distillation (3.0 g, 73 % yield).
63.2% With hydrogen fluoride; antimonypentachloride; at 70 - 200℃; under 63756.4 Torr; for 30h; 500 g (3.08 mol) of 2-chloro-5-chloromethylpyridine (molecular weight: 162 g / mol) and 50 g (10% by weight) of copper oxide were charged into a 1 L four-necked flask equipped with a thermometer, a condenser and a mechanical stir And heated to 275 C, and then chlorinated by passing Cl 2 into the above solution, and the reaction was carried out for 60 hours to obtain 562 g (2.12 mol) of <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong>. A solution of 562 g (2.12 mol) of <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong> was heated to 70 C and added with 5 g of catalyst antimony pentachloride followed by 210 g (10.5 mol) of hydrogen fluoride at 200 C, 8.5 MPa pressure for 30 hours to give 421 g (1.95 mol) of 2,3-dichloro-5-trifluoromethylpyridine in a yield of 63.2% from 2-chloro-5-chloromethylpyridine,
With FeCl2; EXAMPLE 10 2,3-Dichloro-5-(trifluoromethyl)pyridine STR12 A 360 milliliter (ml) TEFLON PFA reaction flask, fitted with a PFA reflux condenser, an HF bleed tube, a magnetic stirrer and an optical pyrometer, was charged with 180 grams (g) of <strong>[69045-83-6]2,3-dichloro-5-(trichloromethyl)pyridine</strong> and 4.3 g (5 mole percent) of FeCl2. Anhydrous HF gas was introduced into the reaction mixture (~4 g/hr) below the surface of the liquid as the reaction mixture was heated to a temperature between 170 C. and 175 C. This temperature (170-175 C.) was maintained for a period of 70 hours with constant agitation. Standard gas-liquid chromatography (GLC) analysis of the product indicated that the reaction product contained:
With hydrogen fluoride; EXAMPLE 7 This Example illustrates the preparation of 2,3-dichloro-5-trifluoromethylpyridine by fluorination of <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong>, using a fluorinating agent alternative to that of Example 6. 2,3-Dichloro-5-trichloromethylpyridine (35 g) was heated with anhydrous hydrogen fluoride (100 g) in an autoclave at 200 for 10 hours with stirring. The cooled reaction mixture was poured on to ice and neutralised with sodium hydroxide at 0. The mixture was extracted with methylene chloride (750 ml). The extracts were washed with water (500 ml), sodium carbonate solution (500 ml) and water (500 ml), dried, and evaporated. The remaining oil was distilled and the fraction of boiling point 77-83/25 Torr was collected and identified as the required pyridine derivative.
With hydrogen fluoride; at 170℃; for 11h; Take intermediate <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong> 50g,After adding the catalyst, the temperature is raised to 170C.Slowly introduce anhydrous hydrogen fluoride gas,Reaction 11h, after the end of the reaction, neutralized with 5% sodium bicarbonate solution,Separate the organic phase, washed,The crude product obtained after drying was 2,3-dichloro-5-trifluoromethylpyridine as the desired material in an amount of 85% and the yield was 65%.

  • 3
  • [ 69045-83-6 ]
  • [ 79456-26-1 ]
  • 4
  • [ 69045-83-6 ]
  • [ 76041-71-9 ]
  • 5
  • [ 69045-83-6 ]
  • [ 76041-74-2 ]
  • 6
  • [ 69045-83-6 ]
  • [ 89570-82-1 ]
  • 7
  • [ 69045-83-6 ]
  • [ 54127-31-0 ]
YieldReaction ConditionsOperation in experiment
79% With acetic acid; zinc; In methanol; at -5℃; for 4h; 2, 3-dichloro-5-trichloromethylpyridine (36.60 g, 0.139 mol) was added to a flask containing acetic acid (53.50 g, 0.892 mol) and methanol (200 mL). The mixture was cooled to-5 C, and zinc dust (20.01 g, 0.308 mol) was added in small portions at 10 minute intervals. The mixture was stirred mechanically for 4 hours, filtered, and concentrated in vacuo. The residue was dissolved in dichloromethane and washed with brine, followed by saturated aqueous sodium bicarbonate, followed by a second brine wash. The organic phase was dried over magnesium sulfate and concentrated in vacuo to yield 21.55 g (79%) of Preparatory Compound P, 2, 3-DICHLORO-5- (CHLOROMETHYL) pyridine, as a yellow liquid (about 65% PURITY). 1H NMR No. 8.31 (d, 1H, J=2.3 Hz), 7.85 (q, 1H, J=0.4 Hz and J=2.2 Hz), 4.56 (s, 2H). MS (ESI) NIZ 199 ([M+4] +, 8), 197 ([M+2]+, 27), 195 ([M]+, 28), 164 (11), 162 (66), 160 (100), 124 (19)
  • 8
  • [ 108-99-6 ]
  • 2-chloro-3-(dichloromethyl)-pyridine [ No CAS ]
  • [ 55366-30-8 ]
  • [ 3099-50-1 ]
  • [ 69045-78-9 ]
  • [ 72648-12-5 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With chlorine;pelletized catalyst TOSOH HSZ-690 HOD (SAR 203) with a silica binder; at 350℃;Gas phase;Product distribution / selectivity; Example 2; The pelletized catalyst, TOSOH HSZ-690 HOD (SAR 203) with a silica binder, was ground to a coarse powder and screened to obtain a uniform size of 1-2 mm in diameter. A weight of 0.26 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. Operating at a chlorine feed of 5 cc/min, a beta-picoline feed rate of 0.13 mg/min (10 cc/min N2 with a chiller temperature of 10 C.), the reagents were fed to the reactor at an initial temperature of 250 C. The system was initially ramped up to 325 C. and allowed to stablize. Under these conditions the product gases were 18.5% 3-trichloromethylpyridine (beta-tri ) and 65.4% beta-2-tet. When the system was allowed to stabilized at 350 C. the amount of beta-tri in the product gases was reduced to 2.6% and the conversion to beta-2-tet increased to 68.6% (see Table 2).; Example 3; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm in diameter. A weight of 0.26 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.13 mg/min (N2 flow 10 cc/min, chiller at 10 C.), while the reactor oven was ramped up to 350 C. over a one hour time period. At 350 C. the amount of beta-2-tet observed in the product gases was 65.6% (see Table 2).; Example 4; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm in diameter. A weight of 0.51 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.13 mg/min (chiller at 10 C.), with a nitrogen flow of 10 cc/min, while the reactor oven was ramped up to 350 C. over 2 hours. When the system had stabilized at 350 C. the amount of beta-2-tet observed in the product gases was 71.7% (see Table 2).; Example 5; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm. A weight of 0.51 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.25 mg/min (N2 at 10 cc/min, chiller at 20 C.), while the reactor oven was slowly ramped up to 350 C. over 2 hours. When the system had stabilized at 350 C. the amount of beta-2-tet observed in the product gases was 66.9% (see Table 2).
With chlorine; at 400℃;Gas phase;Product distribution / selectivity; Example A; This is the control run where the reactor contained glass wool (Pyrex) plugs and no catalyst. The reactor temperature was initially set to 350 C. prior to feeding chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.25 mg/min (N2 at 10 cc/min, chiller at 20 C.) at the oven temperature of 350 C. When the system had stabilized the amount of beta-2-tet was only 8.7%, with the majority of the conversion going to beta-tri (65.4%). When the temperature was increased to 400 C. the amount of beta-2-tet increased to 46.1% with a reduction in beta-tri (21.5%). A fair amount of over chlorinated 2,6-dichloro-3-trichloromethylpyridine (beta-2,6-penta,12.2%) was also observed (see Table 2).
YieldReaction ConditionsOperation in experiment
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound.
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound.
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound.
The product from paragraph (i) (2.9 g) in dry carbon tetrachloride (250 ml) was treated with dry hydrogen chloride to convert it to the hydrochloride. Chlorine was passed through the suspension which was kept at 80 C. and illuminated by an ultra-violet lamp inside the reaction flask. After three hours the solvent was removed, leaving a residue of 2,3-dichloro-5-trichloromethylpyridine.

  • 10
  • [ 824-72-6 ]
  • [ 54127-63-8 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With phosphorus pentachloride; EXAMPLE III Preparation of 2,3-dichloro-5-(trichloromethyl)pyridine STR5 To a 5-liter flask equipped with an air stirrer, thermometer, and condenser was added 1000 grams (5.13 m) of phenylphosphonic dichloride. Thereafter, 383 g (2.707 m) of 5-chloro-6-hydroxynicotinic acid (prepared by bubbling chlorine into a stirred aqueous suspension of 6-hydroxynicotinic acid) was added. The mixture was slowly heated and stirred over a 20 minute period, with the temperature rising to 73 C. The mixture was in the form of a thick paste. To this mixture was slowly added 1755 g (8.4 m) of phosphorus pentachloride over a 45 minute period. The hydrogen chloride by-product which formed was continuously removed and the heat was adjusted to maintain the temperature in the range of 83-108 C. After the phosphorus pentachloride addition was complete, the mixture was heated to reflux and some of the phosphorus oxychloride by-product which formed was allowed to distill off. After a period of about 70 minutes, the temperature had exothermically risen to 169 C. and the temperature was held in the range of 162-180 C. for 53/4 hours. During the above time additional phosphorus oxychloride was intermittently removed. The mixture was allowed to stand overnight and then poured over cracked ice, neutralized with 50 percent sodium hydroxide solution and the product extracted with hexane. The solvent was removed by evaporation under reduced pressure leaving 567 g of crude 2,3-dichloro-5-(trichloromethyl)pyridine. The crude product was placed on a 15 tray vacuum jacketed Oldershaw distillation column and the light ends removed. The pot material was transferred to a Vigreux Claisen still and flash distilled to yield of 518 g (88.5 percent of theoretical) of a colorless oil which analyzed as 99 percent pure 2,3-dichloro-5-(trichloromethyl)pyridine.
  • 11
  • [ 7783-56-4 ]
  • [ 69045-83-6 ]
  • [ 69045-84-7 ]
YieldReaction ConditionsOperation in experiment
With antimonypentachloride; EXAMPLE 8 This Example further illustrates the preparation of 2,3-dichloro-5-trifluoromethylpyridine. Antimony trifluoride (61 g) was melted under a vacuum to remove moisture. The cooled material was broken up and heated to 65-70 while antimony pentachloride (6.6 g) was added dropwise with stirring. 2,3-Dichloro-5-trichloromethylpyridine (40 g) was then added dropwise to the mixture and the whole heated to 160 over 45 minutes. The mixture was cooled and steam distilled. The oil which distilled over was extracted with ether (2*100 ml). The ether extract was washed with tartaric acid solution then water, sodium bicarbonate, and water, and dried. The remaining oil was distilled. The fraction boiling at 71-80/18 Torr was identified as the required pyridine derivative.
  • 12
  • [ 812-22-6 ]
  • [ 107-13-1 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
copper(I) chloride; In tantalum; diethyl ether; acetonitrile; EXAMPLE 5 Single-step preparation of 2,3-dichloro-5-trichloromethylpyridine 23 g of pentachloropropionaldehyde, 8 g of acrylonitrile, 0.5 g of copper(I) chloride and 40 ml of acetonitrile are heated in a tantalum autoclave for 3 hours to 170 C. After they have cooled, the contents of the autoclave are taken up in 50 ml of diethyl ether and the ethereal solution is filtered. The filtrate is evaporated to dryness in vacuo and the residue is rectified. 2,3-Dichloro-5-trichloromethylpyridine is collected in a receiver (yield: 17.49 g). Boiling point: 147-149 C./1700 Pa. IR spectrum (KBr) in cm-1: 3050, 1590, 1555, 1430, 1380, 1180, 1049. 1 H-NMR spectrum (100 MHz in CDCl3) in ppm: 8.85 (d, J=5 Hz), 8.25 (d. J=5 Hz). Elemental analysis for C6 H2 Cl5 N (mol.wt. 265.35): calculated C 27.15%, H 0.75%, N 5.27%, Cl 66.80%; found C 27.1%, H 0.9%, N 5.3%, Cl 66.4%.
  • 13
  • [ 69045-78-9 ]
  • [ 7440-33-7 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
The liquid was found to contain 17 ppm tungsten. The solid (1.4 grams) was used to catalyze the chlorination of 187.6 grams of 2-chloro-5-trichloromethylpyridine at 200 C. and ambient pressure. In 98 hours, 77.5 weight percent of 2,3-dichloro-5-trichloromethylpyridine was obtained.
  • 14
  • 5-chloro-3-trichloromethyl pyridine [ No CAS ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
EXAMPLE 11 This example illustrates the conversion of 5-chloro-3-trichloromethyl pyridine to 5,6-dichloro-3-trichloromethyl pyridine by liquid phase chlorination. One hundred grams of a mixture rich in 5-chloro- and 5,6-dichloro-3-trichloromethyl pyridine was chlorinated in the liquid phase to a mixture richer in 5,6-dichloro-3-trichloromethyl pyridine and in 2,5,6-trichloro-3-trichloromethyl pyridine. TABLE EIGHT illustrates the results.
With phosphorus pentachloride; at 210℃; for 16h;Autoclave; EXAMPLE 9 Preparation of 2,3-dichloro-5-(trichloromethyl)pyridine from various compounds of the formula [I]. The starting material of formula [I] (50 mmole) and PCI5 (1 or 2 eq.) was mixed in a 50 ml teflon autoclave. The autoclave was closed and heated in a 210 C warm metal block. After 16 hours the autoclave was cooled to 25 C and opened. The resulting solution was analysed by GC with results according to table 5. (trichloromethyl)pyridine In comparison, starting with the compound 2-chloro-5- (trichloromethyl)pyridine only very low conversion to the compound [II] is observed.
  • 15
  • [ 3099-50-1 ]
  • 5-chloro-3-trichloromethyl pyridine [ No CAS ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With phosphorus pentachloride; at 210℃; for 16h;Autoclave; EXAMPLE 9 Preparation of 2,3-dichloro-5-(trichloromethyl)pyridine from various compounds of the formula [I]. The starting material of formula [I] (50 mmole) and PCI5 (1 or 2 eq.) was mixed in a 50 ml teflon autoclave. The autoclave was closed and heated in a 210 C warm metal block. After 16 hours the autoclave was cooled to 25 C and opened. The resulting solution was analysed by GC with results according to table 5. (trichloromethyl)pyridine In comparison, starting with the compound 2-chloro-5- (trichloromethyl)pyridine only very low conversion to the compound [II] is observed.
  • 16
  • [ 3099-50-1 ]
  • [ 69045-83-6 ]
  • 17
  • [ 59-67-6 ]
  • 5-chloro-3-trichloromethyl pyridine [ No CAS ]
  • [ 3099-50-1 ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With phosphorus pentachloride; at 175℃; under 18751.9 - 30003 Torr; for 96h;Autoclave; EXAMPLE 5 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out with 4 molar eq. of PCI5 at various temperatures and a pressure reaching between 25 and 40 bar after completion. Results are provided in table 2.
  • 18
  • [ 59-67-6 ]
  • [ 3099-50-1 ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With phosphorus pentachloride; at 185℃; under 18751.9 - 30003 Torr; for 72h;Autoclave; EXAMPLE 5 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out with 4 molar eq. of PCI5 at various temperatures and a pressure reaching between 25 and 40 bar after completion. Results are provided in table 2.
  • 19
  • [ 59-67-6 ]
  • 5-chloro-3-trichloromethyl pyridine [ No CAS ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With phosphorus pentachloride; at 185℃; under 18751.9 - 30003 Torr; for 64h;Autoclave; EXAMPLE 6 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out using various amounts of PCI5, at a temperature set at 210C, and at pressure reaching between 25 and 40 bar after completion. Results in accordance with the below table 3.
  • 20
  • [ 59-67-6 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
75% With chlorine; phosphorus trichloride; at 120 - 180℃; under 2250.23 - 12001.2 Torr;Autoclave; EXAMPLE 10 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Nicotinic acid (50 g, 0.4 mole) and phosphorous trichloride (223 g, 1.6 mole) were added to an 0.5 L jacketed autoclave, connected to a cooling- heating circulator. The temperature of the reaction mixture was adjusted to 120 C and chlorine gas (115 g, 1.6 mole) was added to head space from a pressure bottle. During addition of chlorine was the temperature maintained between 120 C and 140 C with cooling circulation on the jacket. After addition of chlorine gas is the pressure in the autoclave around 3 bar. The temperature is increased to 180 C (will be preferred to increase to 210 C, but this was not possible in the current setup) and kept there for 144 hours (210 C will finish reaction in 16 hours). During the reaction HCl(g) was removed through a scrubber periodically to keep pressure between 12 and 16 bar. The autoclave was then cooled to 25 C and ventilated to a Caustic Lye scrubber. The resulting solution was heated to reflux to recover phosphorous trichloride by distillation. The autoclave was closed again and chlorine gas (50 g, 0.5 mole) was added at room temperature. The resulting mixture was heated to 130 C and pressure was kept below 15 bar by removing HCl(g) above a condenser to a caustic lye scrubber. When pressure becomes stable (typically after 2 - 4 hours), the reaction is considered completed and the autoclave cooled down. If analysis shows otherwise, the final chlorination procedure can be repeated. The reaction mixture was then transferred to a round bottomed flask and phosphoryl chloride was removed by distillation. In case there is any solid PC15 in the reactor, it can be converted to phosphoryl chloride with a few drops of water and transferred together with the main reaction mixture. Upon distillation of phosphoryl chloride - the crude product was obtained by addition to ice cold water, stirred for 10 minutes and allowed to stand for separation for 1 hours at 25 C. The lower organic phase is separated from the acidic water phase and the product hereafter distilled to give 80 g of 2,3-dichloro-5-(trichloromethyl)pyridine with a purity of 96% (75% yield).
  • 21
  • [ 59-67-6 ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
33%Chromat.; 60%Chromat. With phosphorus pentachloride; at 210℃; under 1500.15 - 27752.8 Torr; for 14h;Autoclave; EXAMPLE 7 Conversion of Nicotinic acid to a mixture of 2-chloro-5- (trichloromethyl)pyridine and 2,3-dichloro-5-(trichloromethyl)pyridine. To a 250 ml Berghof autoclave with PTFE lining was added Nicotinic acid (20g, 162 mmole) and phosphorous pentachloride (139 g, 668 mmole). The autoclave was closed and heated to 210 C for 14 hours. During the heating an exotherm was observed around a temperature of 130 C bringing the temperature to 190 C and a pressure increase from 2 bar to 8 bar within 2 minutes. The heating was continued to 210 C. After the 14 hours the pressure had increased to 37 Bar. The autoclave was cooled to room temperature, ventilated to a scrubber, opened and quantified by GC indicating a yield of 2- chloro-5-(trichloromethyl)pyridine of 33% compared to the Nicotinic acid starting material and a yield of 2,3-dichloro-5-(trichloromethyl)pyridine 60%.
  • 22
  • [ 69045-83-6 ]
  • [ 79622-59-6 ]
  • 23
  • C52H56O7 [ No CAS ]
  • [ 69045-83-6 ]
  • C58H57ClF3NO7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
General procedure: To a solution of compound 4 (1 equiv) in dry DMF (4 mL) was addedNaH (60% dispersion in mineral oil) (1.5 equiv) at 0 C. After1 h, R-Cl (b, e-k) (1.5 equiv) was added. The reaction mixture was stirred overnight. The reaction was quenched with icewater and extracted with EtOAc. The organic phase waswashed with water and brine, dried over Na2SO4, and concentrated.The residue was purified by chromatography over silicagel using a gradient of 2:8 ethyl acetate/hexane gave target compounds.
  • 24
  • [ 70258-18-3 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
79% With manganese(IV) oxide; iron(III) chloride; chlorine; at 120℃; under 760.051 Torr; for 45h; At 1 atmosphere,20 g of 2-chloro-5-chloromethylpyridine (0.12 mol) and 0.5 g of manganese dioxide 0.5 g of ferric chloride were heated to 120 C, and chlorine gas was introduced into the mixture for 45 hours.Using GC-MS tracking, it was found that 36% of the starting material was converted to 2,3-dichloro-5-trichloromethylpyridine.When the temperature of the reaction system is heated to 170 C, chlorine gas is continuously introduced for 7 hours.GC-MS trace detection revealed that the starting material had reacted completely.The reaction mixture was diluted with n-hexane, washed with aqueous sodium carbonate and the organic layer was separated.Drying over anhydrous sodium sulfate and removing the solvent by distillation.25.4 g of a yellow liquid 2,3-dichloro-5-trichloromethylpyridine was obtained.The yield was 79%.
562 g With chlorine; copper(II) oxide; at 275℃; for 60h; 500 g (3.08 mol) of 2-chloro-5-chloromethylpyridine (molecular weight: 162 g / mol) and 50 g (10% by weight) of copper oxide were charged into a 1 L four-necked flask equipped with a thermometer, a condenser and a mechanical stir And heated to 275 C, and then chlorinated by passing Cl 2 into the above solution, and the reaction was carried out for 60 hours to obtain 562 g (2.12 mol) of 2,3-dichloro-5-trichloromethylpyridine. A solution of 562 g (2.12 mol) of 2,3-dichloro-5-trichloromethylpyridine was heated to 70 C and added with 5 g of catalyst antimony pentachloride followed by 210 g (10.5 mol) of hydrogen fluoride at 200 C, 8.5 MPa pressure for 30 hours to give 421 g (1.95 mol) of 2,3-dichloro-5-trifluoromethylpyridine in a yield of 63.2% from 2-chloro-5-chloromethylpyridine,
  • 25
  • [ 69045-83-6 ]
  • 3-chloro-2-hydrazino-5-trichloromethylpyridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With hydrazine hydrate; In ethanol; at 30℃; for 5h; After adding 26.5 g (0.1 mol) of 2,3-dichloro-5-trichloromethyl pyridine and 16 g (0.4 mol) of hydrazine hydrate 80% to the reaction kettle, 1000 ml of absolute ethanol was added and reacted at 30 C for 5 hours. Using HPLC analysis, after passing the control, The solvent is distilled off and the product is filtered under reduced pressure to give <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong>. The product yield is 95% and the purity is 99.15%.
  • 26
  • [ 108-99-6 ]
  • [ 69045-83-6 ]
  • 27
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
90% With chlorine; at 150 - 160℃; for 6h; The obtained 2-chloro-5-trichloromethylpyridine 46.2 g,After adding the catalyst, the temperature is raised to 150-160C.Slowly dry the chlorine gas for heavy chlorination.After 6 hours of reaction, dilute the reaction solution with benzene, wash with water and dry the organic phase.After evaporating the benzene under reduced pressure,After distillation, 50.3 g of oily product was obtained.That is the intermediate 2,3-dichloro-5-trichloromethylpyridine,The yield was 90% and the content was 95%.
With chlorine; at 130 - 180℃; for 100h;Large scale; 2000 kg of 2-chloro-5-trichloromethylpyridine was placed in a glass-lined chlorination kettle.Then adding catalyst to the reactorThe 150kg reactor is heated with a heat transfer oil.When the temperature rises to 130 C, chlorine gas is introduced into the reactor to control the amount of chlorine.The reaction temperature was controlled at 180 C. The reaction time is usually 100 hours.After the reaction is completed, the temperature is lowered to 50 C, and the catalyst is filtered off.After the 2,3-dichloro-5-trichloromethylpyridine was metered, it was fluorinated in a fluorination kettle.
  • 28
  • [ 69045-83-6 ]
  • 3,5-dichloro-4-[(3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy]aniline [ No CAS ]
  • 29
  • [ 69045-83-6 ]
  • chlorfluazuron [ No CAS ]
  • 30
  • [ 69045-83-6 ]
  • [ 72537-17-8 ]
YieldReaction ConditionsOperation in experiment
97.56% 1. In a 200 mL autoclave, add 23.0 g (0.1 mol) of 2,3,-dichloro-5-trichloromethylpyridine, place a lid on the kettle, and fill it with nitrogen for 1 hour at a pressure of 10.0 MPa for 5 hours to leak the reaction kettle. After confirming that the reactor is leak-free, the pressure in the kettle is vented.The reactor was then placed in an ice-salt bath and cooled when the temperature in the kettle fell below -5C.The kettle was charged with anhydrous HF 40.0 g (~2.0 mol), and the reaction system was heated to 180C with stirring, and the reaction was incubated for 12 hours.2. After the reaction is completed, cool down to 25C, exchange nitrogen in the reactor for half an hour (exchanged gas is passed into 10% aqueous sodium hydroxide for neutralization absorption), and hydraulically introduce the reaction into a 250 mL round bottom flask. ,70 g (~1.0 mol) of a 25% aqueous ammonia solution was added and reacted at 35C for 12 hours under normal pressure.3. After the reaction is complete, collect the oil layer and wash three times until neutral. Add 10g of anhydrous sodium sulfate to the oily liquid and dry it for 6h. Filter the solids out and then conduct vacuum distillation to collect the fraction with a boiling point of 50-55C/11mmHg.Obtained 16.0 g of 2-fluoro-3-chloro-5-trifluoromethylpyridine product.The content of 2-fluoro-3-chloro-5-trifluoromethylpyridine in the product was determined to be 99.95% (GC) and the yield was 97.56%.
With hydrogen fluoride; antimony pentafluoride; at 180℃; under 45004.5 Torr; for 24h;Large scale; The chlorinated <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong> was put into a fluorination kettle (about 2300 kg).Injecting catalyst into the reaction fluorineAntimony pentafluoride 200kg,Add 1700kg of anhydrous hydrogen fluoride,The molar ratio of <strong>[69045-83-6]2,3-dichloro-5-trichloromethylpyridine</strong> to hydrogen fluoride is 1:10.Excessive hydrogen fluoride facilitates the reaction.Turn on the reactor and stir, heat up and keep at 180 C.The reaction was carried out at a pressure of 6 MPa for 24 hours, and the temperature was lowered to 60 C.Transfer the material to 3000L in advanceWater in the washing kettle,The material is washed twice and then neutralized to a pH of 7,The material is then layered into a rectification tank.The mixture was subjected to vacuum distillation to obtain 2-fluoro-3-chloro-5-trifluoromethylpyridine having a content of ?99%.
  • 31
  • [ 108-99-6 ]
  • [ 3099-31-8 ]
  • [ 69045-78-9 ]
  • [ 72648-12-5 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
47%Chromat.; 21%; 4.8%Chromat.; 11%Chromat. With tetrachloromethane; at 200 - 350℃; for 0.00305556h;Molecular sieve; Inert atmosphere; 40 G ZSM - 5 molecular sieve (silicon-aluminum ratio 200, strip (1 - 2 mm)) by adding [...] 60 cm, diameter of 2.4 cm cylindrical quartz tube, the upper end of the catalyst filling 10 g of inert ceramic ball (diameter 4 mm), the quartz tube using the resistance wire heating. The constant pressure in the funnel 8 g 3 - methyl pyridine and 70 g CCl4[...] 200 C flask, 2 h the raw materials of the completion of the dropping, of the 3 - methyl pyridine with CCl4The steam is N2The carrier gas to the quartz tube, N2The flow rate control in 250 ml/min. Cl2In order to 300 ml/min flow rate individually to the quartz tube with the raw material of the steam in the catalyst bed on the reaction, the reaction temperature is 350 C, time is 11 s. The reaction mixture through the receiving flask condensation, GC normalized 3 - methyl pyridine totally transformed, 3 - dichloro pyridine and isomer 47%, 2 - chloro -5 - trichloromethyl pyridine 27%, 2 - chloro -3 - trichloromethyl pyridine 4.8%, 2, 3 - dichloro -5 - trichloromethyl pyridine 11%. The purity of the purification after rectification>99% of 2 - chloro -5 - trichloromethyl pyridine, the yield of 21%.
  • 32
  • [ 108-99-6 ]
  • [ 6515-09-9 ]
  • [ 69045-78-9 ]
  • [ 69045-83-6 ]
YieldReaction ConditionsOperation in experiment
With chlorine; In tetrachloromethane; at 400℃; for 4h; 10 g of catalyst B was taken into a cylindrical fixed bed reactor with an inner diameter of 25 mm, and the plunger pump was pumped into a solution of 3-methylpyridine in carbon tetrachloride. The mass ratio of 3- methylpyridine to carbon tetrachloride was 1: The weight hourly space velocity of 10,3-methylpyridine is 6h, the chlorine gas flow rate is 2L/min, and the 3-methylpyridine and chlorine gas are vaporized by the preheating tube and then passed into the fixed bed reactor. The fixed bed reactor is used. The temperature was 400 C, the reaction was carried out for 4 h, the reaction product was passed through a condenser, and 2987 g of the reaction product mixture was obtained in a receiving tank. The ammonia solution was added to adjust to neutrality, and the pear-shaped funnel was separated to obtain an organic phase. 30 g of anhydrous sulfuric acid was added to the organic phase. Magnesium is dehydrated, suction filtered, and then rotary evaporated to remove carbon tetrachloride to give a pale yellow liquid. After analysis and detection, the product is a mixture of 2-chloro-5-trichloromethylpyridine, 2,3-dichloro-5-trichloromethylpyridine and 2,3,6-trichloropyridine, respectively. 77%, 16%, 7%. It is indicated that it is difficult to remove trichloromethyl group under the reaction conditions in the absence of water
 

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