CN104356053B - Preparation method of 2-(3-halogen phenyl) pyridine derivative - Google Patents
Preparation method of 2-(3-halogen phenyl) pyridine derivative Download PDFInfo
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- CN104356053B CN104356053B CN201410563504.4A CN201410563504A CN104356053B CN 104356053 B CN104356053 B CN 104356053B CN 201410563504 A CN201410563504 A CN 201410563504A CN 104356053 B CN104356053 B CN 104356053B
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
Abstract
The invention discloses a preparation method of a 2-(3-halogen phenyl) pyridine derivative. The preparation method comprises the following steps: dissolving 2-phenylpyridine or substitutive 2-phenylpyridine (I) and N-halogenated butyl diimide (II) into a solvent, adding a ruthenium catalyst for reaction at the temperature of 70-150 DEG C for 24-48 hours to obtain a mixture, extracting with ethyl acetate, separating and purifying the mixture by column chromatography after the mixture is washed and dried to obtain the 2-(3-halogen phenyl) pyridine derivative (III), wherein the reaction formula of the 2-(3-halogen phenyl) pyridine derivative is shown in the specification. The preparation method has the advantages of simplicity in operation, higher yield and the like; furthermore, reaction raw materials and reaction reagents are readily available, and multiple types of product substitutes are produced.
Description
Technical field
The present invention relates to the preparation method of 2- (3- halogen phenyl) pyridine derivatives.
Background technology
Aryl halide is the important chemical intermediate of a class, and it can be introduced different by transition metal-catalyzed coupling
Functional group, synthesizes complex compound, as some complicated native compounds or medicine.The side of introducing halogen classical in the past
Method mainly has the nucleophilic substitution of aromatic ring and the halogenating reaction of transistion metal compound intermediate.They can only be in supplied for electronic
Ortho para position introduces halogen.The phenyl ring that electron withdraw group replaces, due to the passivation of electron-withdrawing group, introduces the example of halogen in meta
Son is considerably less.Therefore, exploitation one kind can high regioselectivity, meta introduce aromatic ring halogen method be that there is meaning very much
's.
As a kind of aryl halogenation strategy of supplement, the transition metal-catalyzed introducing halogen facing position guiding and high selectivity
Element has been developed as a kind of new effective ways.At present, the metal being applied to this field includes palladium, gold, ruthenium, rhodium and copper.
It is emphasized that pyridine radicals transition metal-catalyzed facing be proved to be in a halogenation relatively effective guiding base it
One.
Recently, frost and ackermann report respectively transition metal ruthenium catalysis meta optionally build carbon-sulfur bond
And carbon-carbon bond.But they do not realize the structure of carbon-halogen bond.
[1]a.f.littke,g.c.fu,angew.chem.2002,114,4350-4386；
angew.chem.int.ed.2002,41,4176-4211；
[2]p.b.de la mare,electrophilic halogenation,cambridge university
press,cambridge,1976,chap.5.
[3]v.snieckus,chem.rev.1990,90,879–933.
[4]d.kalyani,a.r.dick,w.q.anani,m.s.sanford,org.lett.2006,8,2523–
2526.
[5]a.r.dick,k.l.hull,m.s.sanford,j.am.chem.soc.2004,126,2300-2301；
[6]f.y.mo,j.m.yan,d.qiu,f.li,y.zhang,j.b.wang,angew.chem.int.ed.2010,
49,2028–2032.
[7]n.j.wencel-delord,f.glorius,j.am.chem.soc.2012,134,8298–
8301.
[8]l.h.wang,l.ackermann,chem.commun.2014,1083-1085.
[9]l.menini,e.v.gusevskaya,chem.commun.2006,209–211
However, aryl halogen is selectively introducing by the meta that transition metal ruthenium is catalyzed synthesize 2- (3- halogen phenyl) pyridine
The method of analog derivative it is not yet reported that.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides a kind of 2- (3- halogen phenyl) pyridine derivatives
Preparation method.
Technical scheme is summarized as follows:
The preparation method of 2- (3- halogen phenyl) pyridine derivatives, comprises the steps: 2- phenylpyridine or replacement
2- phenylpyridine (i), n- N-halosuccinimides (ii) are dissolved in solvent, add ruthenium catalyst to react 24-48 in 70-150 DEG C
Hour, be extracted with ethyl acetate, wash, be dried after through column chromatography separating purification, obtain 2- (3- halogen phenyl) pyridines derive
Thing (iii)；Its reaction equation is:
Wherein r1For hydrogen, fluorine, chlorine, bromine, methyl, benzyl, isopropyl, the tert-butyl group, phenyl or methoxyl group；
r2For hydrogen, fluorine, chlorine, bromine, iodine, methyl, methoxyl group, vinyl, ethyoxyl formyl ester group or trifluoromethyl；
X is chlorine, bromine or iodine；
Ruthenium catalyst is bivalence ruthenium catalyst or trivalent ruthenium catalyst.
Replace 2- phenylpyridine (i) and be preferably 2- (4- aminomethyl phenyl) pyridine, 2- (4- methoxyphenyl) pyridine, 2- (2-
Methoxyphenyl) pyridine, 2- (2- aminomethyl phenyl) pyridine, 2- (4- fluorophenyl) pyridine, 2- (4- chlorphenyl) pyridine, 2- (4- bromine
Phenyl) pyridine, 2- (4- iodophenyl) pyridine, 2- (4- ethenylphenyl) pyridine, 2- (4- ethyoxyl formylphenyl) pyridine, 2-
(4- trifluoromethyl) pyridine, 2- phenyl -4- methvl-pyridinium, 2- phenyl -4- benzyl-pyridine, 2- phenyl -4- isopropyl-pyrrole
Pyridine, 2- phenyl -4- tert-Butyl-pyridin, 2- phenyl -4- methoxv-pyridine, the fluoro- pyridine of 2- phenyl -4-, the chloro- pyrrole of 2- phenyl -4-
Pyridine, the bromo- pyridine of 2- phenyl -4-, 2- phenyl -3- methvl-pyridinium, 2- phenyl -4- phenyl-pyridin.
Ruthenium catalyst preferably (4- cymene) ruthenous chloride dimer, (1,5- cyclo-octadiene) ruthenous chloride,
Lattice granny rag catalyst, (1.2.3.4.5- pentamethylcyclopentadiene) ruthenous chloride polymer, ruthenium trichloride.
Solvent is estimated and is elected n as, n- dimethyl acetylamide, n, n- dimethylformamide, n- methyl pyrrolidone, Isosorbide-5-Nitrae-dioxy six
Ring, acetonitrile or dichloroethanes.
The present invention has simple to operate, and reaction raw materials and reaction reagent are easy to get, and product replaces that base type is various, and yield is relatively
High the advantages of.
Specific embodiment
The synthetic method reaction equation of 2- (3- halogen phenyl) pyridine derivatives (iii) of the present invention is:
Required reaction raw materials 2- phenylpyridine (i) in each embodiment, are that reference literature method prepares (a.khalafi-
nezhad,f.panahi,green chem.2011,13,2408–2415.)
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The preparation of 2- (3- bromophenyl) pyridine (iii-a):
By 2- phenylpyridine (i-a) (47mg, 0.3mmol), n- bromo-succinimide (ii) (108mg, 0.6mmol),
It is dissolved in n, in n- dimethyl acetylamide (0.2m, 1.5ml), addition (4- cymene) ruthenous chloride dimer (9mg,
5mol%), react 24 hours at 70 DEG C, add ethyl acetate (20ml) extraction, washed with water (10mlx3), organic faciess are through no
Aqueous sodium persulfate filters after being dried, and rotation removes solvent, and crude product, through column chromatography separating purification, obtains 2- (3- bromophenyl) pyridine (iii-a)
61mg, is colorless oil, yield: 87%.1h nmr(600mhz,cdcl3): δ 8.70 (t, j=4.8,1h), 8.17 (t, j=
1.6,1h), 7.91 (d, j=7.8,1h), 7.77 (td, j=7.8,1.7,1h), 7.71 (d, j=7.9,1h), 7.54 (dd, j
=7.9,0.9,1h), 7.35 (t, j=7.9,1h), 7.30 7.25 (m, 1h).13c nmr(151mhz,cdcl3)δ154.86,
148.79,140.40,135.90,130.85,129.23,129.02,124.39,122.04,121.66,119.59.
Substitute the n- bromo-succinimide of the present embodiment, other same the present embodiment, experiment with n- chlorosuccinimide
Prove, prepare 2- (3- chlorphenyl) pyridine；Substitute the n- bromo-succinimide of the present embodiment with n- N-iodosuccinimide,
Other same the present embodiment, it is demonstrated experimentally that prepare 2- (3- iodophenyl) pyridine.
Embodiment 2
The preparation of (3- bromo- 4- methoxyphenyl) pyridine (iii-b):
By 2- (4- methoxyphenyl) pyridine (i-b) (56mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in n, in n- dimethylformamide (0.2m, 1.5ml), addition (1,5- cyclo-octadiene) ruthenous chloride (8mg,
10mol%), react 24 hours at 150 DEG C, add ethyl acetate (20ml) extraction, washed with water (10mlx3), organic faciess warp
Filter after anhydrous sodium sulfate drying, rotation removes solvent, crude product, through column chromatography separating purification, obtains (3- bromo- 4- methoxyphenyl) pyridine
(iii-b) 72mg, is colorless oil, yield: 90%.1h nmr(600mhz,cdcl3) δ 8.66 (d, j=4.6hz, 1h),
8.23 (d, j=2.1hz, 1h), 7.93 (dd, j=8.6,2.0hz, 1h), 7.73 (t, j=7.5hz, 1h), 7.65 (d, j=
7.9hz, 1h), 7.20 (t, j=6.0hz, 1h), 6.99 (d, j=8.6hz, 1h), 3.95 (s, 3h).13c nmr(151mhz,
cdcl3)δ156.56,155.68,149.65,136.84,133.30,131.85,127.01,121.95,119.87,112.14,
111.83,56.36.
Embodiment 3
The preparation of 2- (3- bromo- 4- aminomethyl phenyl) pyridine (iii-c):
By 2- (4- aminomethyl phenyl) pyridine (i-c) (51mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in n- methyl pyrrolidone (0.2m, 1.5ml), add Ge Labu catalyst (10mol%), at 100 DEG C
Reaction 48 hours, adds ethyl acetate (20ml) extraction, is washed with water (10mlx3), organic faciess mistake after anhydrous sodium sulfate drying
Filter, rotation removes solvent, and crude product, through column chromatography separating purification, obtains 2- (3- bromo- 4- aminomethyl phenyl) pyridine (iii-c) 67mg, is colourless
Grease, yield: 89%.1h nmr(600mhz,cdcl3) δ 8.61 (d, j=4.4hz, 1h), 8.13 (s, 1h), 7.75 (dd, j
=7.9,1.4hz, 1h), 7.67 (tt, j=9.1,4.6hz, 1h), 7.62 (d, j=7.8hz, 1h), 7.25 (d, j=7.9hz,
1h), 7.16 (t, j=6.6hz, 1h), 2.38 (s, 3h).13c nmr(151mhz,cdcl3)δ155.87,149.73,138.77,
138.64,136.86,131.05,130.71,125.58,125.48,122.38,120.33,22.77.
Embodiment 4
The preparation of 2- (3- bromo- 4- chlorphenyl) pyridine (iii-d)
By 2- (4- chlorphenyl) pyridine (i-d) (57mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in dichloroethanes (0.2m, 1.5ml), add (1.2.3.4.5- pentamethylcyclopentadiene) ruthenous chloride many
Aggressiveness (5mol%), reacts 24 hours at 120 DEG C, adds ethyl acetate (20ml) extraction, is washed with water (10mlx3), organic
Filter after anhydrous sodium sulfate drying, rotation removes solvent, crude product, through column chromatography separating purification, obtains 2- (3- bromo- 4- chlorphenyl) pyrrole
Pyridine (iii-d) 58mg, is white solid, yield: 72%.1h nmr(600mhz,cdcl3) δ 8.69 (d, j=4.6hz, 1h),
8.30 (d, j=2.0hz, 1h), 7.86 (dt, j=19.9,10.0hz, 1h), 7.77 (td, j=7.8,1.6hz, 1h), 7.69
(d, j=7.9hz, 1h), 7.54 (d, j=8.4hz, 1h), 7.32 7.22 (m, 1h).13c nmr(151mhz,cdcl3)δ
154.81,149.87,139.35,137.02,135.09,132.08,130.52,126.66,122.99,122.87,120.40.
With 2- (4- fluorophenyl) pyridine (i-h), 2- (4- bromophenyl) pyridine (i-i), 2- (4- iodophenyl) pyridine (i-j),
2- (4- ethenylphenyl) pyridine (i-k), 2- (4- ethyoxyl formylphenyl) pyridine (i-l) or 2- (4- trifluoromethyl) pyrrole
Pyridine (i-m) substitutes 2- (4- chlorphenyl) pyridine (i-d) of the present embodiment respectively, and other same the present embodiment, it is demonstrated experimentally that prepare
2- (3- bromo- 4- fluorophenyl) pyridine (iii-h), 2- (3- bromo- 4- bromophenyl) pyridine (iii-i), 2- (3- bromo- 4- iodophenyl) pyrrole
Pyridine (iii-j), 2- (3- bromo- 4- ethenylphenyl) pyridine (iii-k), 2- (3- bromo- 4- ethyoxyl formylphenyl) pyridine (iii-
Or 2- (3- bromo- 4- trifluoromethyl) pyridine (iii-m) l).
Embodiment 5
The preparation of 2- (3- bromo- 2- methoxyphenyl) pyridine (iii-e)
By 2- (2- methoxyphenyl) pyridine (i-e) (56mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in acetonitrile (0.2m, 1.5ml), add (1,5- cyclo-octadiene) ruthenous chloride (8mg, 10mol%), 80
React 24 hours at DEG C, add ethyl acetate (20ml) extraction, washed with water (10mlx3), organic faciess are through anhydrous sodium sulfate drying
After filter, rotation removes solvent, and crude product, through column chromatography separating purification, obtains 2- (3- bromo- 2- methoxyphenyl) pyridine (iii-e) 70mg,
For colorless oil, yield: 88%.1h nmr(600mhz,cdcl3) δ 8.71 (d, j=4.2hz, 1h), 7.92 (d, j=
2.6hz, 1h), 7.80 (d, j=8.7hz, 1h), 7.70 (td, j=7.8,1.7hz, 1h), 7.48 7.41 (m, 1h), 7.25
7.19 (m, 1h), 6.87 (d, j=8.8hz, 1h), 3.83 (s, 3h).13c nmr(151mhz,cdcl3)δ156.09,154.57,
149.51,135.83,133.72,132.43,130.87,125.10,122.18,113.49,113.18,55.89.
Embodiment 6
The preparation of 2- (3- bromo- 2- aminomethyl phenyl) pyridine (iii-f)
By 2- (o-tolyl) pyridine (i-f) (51mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in Isosorbide-5-Nitrae-dioxane (0.2m, 1.5ml), add grubbs catalyst (10mol%), anti-at 100 DEG C
Answer 48 hours, add ethyl acetate (20ml) extraction, washed with water (10mlx3), organic faciess mistake after anhydrous sodium sulfate drying
Filter, rotation removes solvent, and crude product, through column chromatography separating purification, obtains 2- (3- bromo- 2- aminomethyl phenyl) pyridine (iii-f) 50mg, is colourless
Grease, yield: 67%.1h nmr(600mhz,cdcl3) δ 8.70 (d, j=4.4hz, 1h), 7.76 (td, j=7.7,
1.6hz, 1h), 7.61 (d, j=7.9hz, 1h), 7.36 (d, j=7.8hz, 1h), 7.33 7.26 (m, 2h), 7.13 (t, j=
7.8hz,1h),2.37(s,3h).13c nmr(151mhz,cdcl3)δ159.60,149.32,142.57,136.31,135.70,
132.57,128.85,126.94,126.51,124.22,122.09,20.64.
Embodiment 7
The preparation of 2- (3- bromophenyl) -4- picoline (iii-g)
By 2- phenyl -4- picoline (i-g) (51mg, 0.3mmol), n- bromo-succinimide (ii) (108mg,
0.6mmol), it is dissolved in acetonitrile (0.2m, 1.5ml), adds ruthenium trichloride (10mol%), react 24 hours at 120 DEG C, plus
Enter ethyl acetate (20ml) extraction, washed with water (10mlx3), organic faciess filter after anhydrous sodium sulfate drying, rotation removes solvent,
Crude product, through column chromatography separating purification, obtains 2- (3- bromophenyl) -4- picoline (iii-g) 73mg, is colorless oil, yield:
85%.1h nmr(400mhz,cdcl3) δ 8.47 (d, j=5.0hz, 1h), 8.07 (t, j=1.7hz, 1h), 7.82 (d, j=
7.8hz, 1h), 7.49 7.41 (m, 2h), 7.25 (t, j=7.9hz, 1h), 7.01 (d, j=7.5hz, 1h), 2.34 (s, 3h)
.13c nmr(151mhz,cdcl3)δ154.73,148.50,146.98,140.53,130.69,129.16,129.00,
124.41,122.66,121.95,120.56,20.20.
With 2- phenyl -4- benzyl-pyridine (i-n), 2- phenyl -4- isopropyl-pyridine (i-o), the 2- phenyl -4- tert-butyl group -
Pyridine (i-p), 2- phenyl -4- methoxv-pyridine (i-q), 2- phenyl -4- fluoro- pyridine (i-r), 2- phenyl -4- chloro- pyridine (i-
S), the bromo- pyridine of 2- phenyl -4- (i-t), 2- phenyl -3- methvl-pyridinium (i-u) or 2- phenyl -4- phenyl-pyridin (i-v) are respectively
Substitute 2- phenyl -4- methvl-pyridinium (i-g) of the present embodiment, other same the present embodiment, it is demonstrated experimentally that prepare 2- (3- bromobenzene
Base) -4- benzyl-pyridine (iii-n), 2- (3- bromophenyl) -4- isopropyl-pyridine (iii-o), 2- (3- bromophenyl) the tertiary fourth of -4-
Base-pyridine (iii-p), 2- (3- bromophenyl) -4- methoxv-pyridine (iii-q), 2- (3- bromophenyl) -4- fluoro- pyridine (iii-
R), the 2- chloro- pyridine of (3- bromophenyl) -4- (iii-s), the 2- bromo- pyridine of (3- bromophenyl) -4- (iii-t), 2- (3- bromophenyl) -
3- methvl-pyridinium (iii-u) or 2- (3- bromophenyl) -4- phenyl-pyridin (iii-v).
The above, be only the section Example of the present invention, and not the present invention is done with any pro forma restriction, all
It is any simple modification, equivalent variations and modification above-described embodiment made according to the technical spirit of the present invention, belong to this
The protection domain of invention.
Claims (2)
- The preparation method of 1.2- (3- halogen phenyl) pyridine derivatives is it is characterised in that comprise the steps: 2- phenyl pyrazoline Pyridine or replacement 2- phenylpyridine (i), n- N-halosuccinimides (ii) are dissolved in solvent, add ruthenium catalyst anti-in 70-150 DEG C Answer 24-48 hour, be extracted with ethyl acetate, wash, be dried after through column chromatography separating purification, obtain 2- (3- halogen phenyl) pyridine Analog derivative (iii)；Its reaction equation is:Wherein r1For hydrogen, fluorine, chlorine, bromine, methyl, benzyl, isopropyl, the tert-butyl group, phenyl or methoxyl group；r2For hydrogen, fluorine, chlorine, bromine, iodine, methyl, methoxyl group, vinyl, ethoxy acetyl or trifluoromethyl；X is chlorine, bromine or iodine；Described replacement 2- phenylpyridine (i) is 2- (4- aminomethyl phenyl) pyridine, 2- (4- methoxyphenyl) pyridine, 2- (2- methoxy Base phenyl) pyridine, 2- (2- aminomethyl phenyl) pyridine, 2- (4- fluorophenyl) pyridine, 2- (4- chlorphenyl) pyridine, 2- (4- bromophenyl) Pyridine, 2- (4- iodophenyl) pyridine, 2- (4- ethenylphenyl) pyridine, 2- (4- ethyoxyl formylphenyl) pyridine, 2- (4- trifluoro Aminomethyl phenyl) pyridine, 2- phenyl -4- methvl-pyridinium, 2- phenyl -4- benzyl-pyridine, 2- phenyl -4- isopropyl-pyridine, 2- benzene Base -4- tert-Butyl-pyridin, 2- phenyl -4- methoxv-pyridine, the fluoro- pyridine of 2- phenyl -4-, the chloro- pyridine of 2- phenyl -4-, 2- benzene The bromo- pyridine of base -4-, 2- phenyl -3- methvl-pyridinium, 2- phenyl -4- phenyl-pyridin；Described ruthenium catalyst is (4- cymene) ruthenous chloride dimer, (1,5- cyclo-octadiene) ruthenous chloride, Ge La Cloth catalyst, (1,2,3,4,5- pentamethylcyclopentadiene) ruthenous chloride polymer, ruthenium trichloride.
- 2. preparation method according to claim 1, is characterized in that described solvent is n, n- dimethyl acetylamide, n, n- diformazan Base Methanamide, n- methyl pyrrolidone, Isosorbide-5-Nitrae-dioxane, acetonitrile or dichloroethanes.
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