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65094-22-6

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65094-22-6 Usage

Uses

Diethyl (bromodifluoromethyl)phosphonate is used as a reactant for the preparation of phosphopeptide mimetic prodrugs targeted to Src homology 2 (SH2) domain of signal transducer and activator of transcription 3 (Stat3), synthesis of Mycobacterium tuberculosis protein tyrosine phosphatase inhibitory difluoromethylphosphonic acid derivatives via multi step synthesis with Suzuki coupling and resolution as key steps and P-C bond cleavage on basic hydrolysis.

Synthesis Reference(s)

The Journal of Organic Chemistry, 49, p. 3437, 1984 DOI: 10.1021/jo00192a056

Check Digit Verification of cas no

The CAS Registry Mumber 65094-22-6 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 6,5,0,9 and 4 respectively; the second part has 2 digits, 2 and 2 respectively.
Calculate Digit Verification of CAS Registry Number 65094-22:
(7*6)+(6*5)+(5*0)+(4*9)+(3*4)+(2*2)+(1*2)=126
126 % 10 = 6
So 65094-22-6 is a valid CAS Registry Number.
InChI:InChI=1/C5H10BrF2O3P/c1-3-10-12(9,11-4-2)5(6,7)8/h3-4H2,1-2H3

65094-22-6 Well-known Company Product Price

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  • TCI America

  • (D3071)  Diethyl (Bromodifluoromethyl)phosphonate  >97.0%(GC)

  • 65094-22-6

  • 5g

  • 770.00CNY

  • Detail
  • TCI America

  • (D3071)  Diethyl (Bromodifluoromethyl)phosphonate  >97.0%(GC)

  • 65094-22-6

  • 25g

  • 2,650.00CNY

  • Detail
  • Alfa Aesar

  • (L16715)  Diethyl (bromodifluoromethyl)phosphonate, 97%   

  • 65094-22-6

  • 1g

  • 233.0CNY

  • Detail
  • Alfa Aesar

  • (L16715)  Diethyl (bromodifluoromethyl)phosphonate, 97%   

  • 65094-22-6

  • 5g

  • 780.0CNY

  • Detail
  • Alfa Aesar

  • (L16715)  Diethyl (bromodifluoromethyl)phosphonate, 97%   

  • 65094-22-6

  • 25g

  • 3226.0CNY

  • Detail
  • Aldrich

  • (411361)  Diethyl(bromodifluoromethyl)phosphonate  96%

  • 65094-22-6

  • 411361-5G

  • 905.58CNY

  • Detail

65094-22-6SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 12, 2017

Revision Date: Aug 12, 2017

1.Identification

1.1 GHS Product identifier

Product name Diethyl (bromodifluoromethyl)phosphonate

1.2 Other means of identification

Product number -
Other names 1-[[bromo(difluoro)methyl]-ethoxyphosphoryl]oxyethane

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:65094-22-6 SDS

65094-22-6Synthetic route

dibromodifluoromethane
75-61-6

dibromodifluoromethane

triethyl phosphite
122-52-1

triethyl phosphite

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

Conditions
ConditionsYield
In tetrahydrofuran at 60℃; for 0.5h;96%
In diethyl ether for 24h; Heating;96%
In diethyl ether for 20h; Heating / reflux;96%
O,O-diethyl 1,1-difluoro-1-bromomethane phosphonothioate
180627-08-1

O,O-diethyl 1,1-difluoro-1-bromomethane phosphonothioate

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

Conditions
ConditionsYield
With perfluoro-cis-2-n-hexyl-3-n-pentyloxaziridine In various solvent(s) for 0.0833333h; Ambient temperature; further reagent;96%
(bromodifluormethyl)triphenylphosphonium bromide
58201-66-4

(bromodifluormethyl)triphenylphosphonium bromide

triethyl phosphite
122-52-1

triethyl phosphite

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

Conditions
ConditionsYield
In dichloromethane for 0.166667h; Ambient temperature;92%
(bromodifluormethyl)triphenylphosphonium bromide
58201-66-4

(bromodifluormethyl)triphenylphosphonium bromide

triethyl phosphite
122-52-1

triethyl phosphite

A

ethyl bromide
74-96-4

ethyl bromide

B

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

C

triphenylphosphine
603-35-0

triphenylphosphine

Conditions
ConditionsYield
In dichloromethane for 0.166667h; Product distribution; Mechanism; Ambient temperature;A n/a
B 92%
C 65%
(bromodifluormethyl)triphenylphosphonium bromide
58201-66-4

(bromodifluormethyl)triphenylphosphonium bromide

triethyl phosphite
122-52-1

triethyl phosphite

A

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

B

triphenylphosphine
603-35-0

triphenylphosphine

Conditions
ConditionsYield
In dichloromethane at 20℃;A 67%
B n/a
halon-1211
353-59-3

halon-1211

triethyl phosphite
122-52-1

triethyl phosphite

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

Conditions
ConditionsYield
at 120℃; under 3811.31 Torr; for 240h; Michaelis-Arbuzov reaction; Autoclave;20%
diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

tert-butyl (E)-3-iodobut-2-enoate
292601-91-3

tert-butyl (E)-3-iodobut-2-enoate

tert-butyl (E)-3-(diethylphosphonodifluoromethyl)but-2-enoate
292601-92-4

tert-butyl (E)-3-(diethylphosphonodifluoromethyl)but-2-enoate

Conditions
ConditionsYield
Stage #1: diethyl (bromodifluoromethyl)phosphonate With zinc In N,N-dimethyl-formamide at 20℃; for 3h; Metallation;
Stage #2: tert-butyl (E)-3-iodobut-2-enoate With copper(I) bromide In N,N-dimethyl-formamide at 20℃; for 3h; Alkylation; cross-coupling; Further stages.;
99.4%
diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

2',6'-dichloro-4'-nitro-[1,1'-biphenyl]-2-ol

2',6'-dichloro-4'-nitro-[1,1'-biphenyl]-2-ol

2,6-dichloro-2'-(difluoromethoxy)-4-nitro-1,1'-biphenyl

2,6-dichloro-2'-(difluoromethoxy)-4-nitro-1,1'-biphenyl

Conditions
ConditionsYield
With potassium hydroxide In water; acetonitrile at -78 - 20℃;99%
diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

triethylamine
121-44-8

triethylamine

Triethyl(difluoromethyl)ammoniumbromid

Triethyl(difluoromethyl)ammoniumbromid

Conditions
ConditionsYield
With methanol; cesium fluoride In dichloromethane at 25℃; for 3h; Inert atmosphere; Sealed tube; chemoselective reaction;99%
diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

<(Ethinyl)(isopropyl)methyl>-p-toluolsulfonat
79157-49-6

<(Ethinyl)(isopropyl)methyl>-p-toluolsulfonat

(1,1-difluoro-5-methyl-hexa-2,3-dienyl)-phosphonic acid diethyl ester
334940-73-7

(1,1-difluoro-5-methyl-hexa-2,3-dienyl)-phosphonic acid diethyl ester

Conditions
ConditionsYield
Stage #1: diethyl (bromodifluoromethyl)phosphonate With copper(I) bromide; zinc In N,N-dimethyl-formamide
Stage #2: <(Ethinyl)(isopropyl)methyl>-p-toluolsulfonat With copper(I) bromide In N,N-dimethyl-formamide at 20℃; for 12h;
98%
4-nitro-phenol
100-02-7

4-nitro-phenol

diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

1-difluoromethoxy-4-nitrobenzene
1544-86-1

1-difluoromethoxy-4-nitrobenzene

Conditions
ConditionsYield
With potassium hydroxide In water; acetonitrile at -78 - 20℃; for 0.333333h;98%
With potassium hydroxide In water; acetonitrile at 25℃; Cooling;
diethyl (bromodifluoromethyl)phosphonate
65094-22-6

diethyl (bromodifluoromethyl)phosphonate

Na+[O2P(OEt)CF2Br]-
1333210-85-7

Na+[O2P(OEt)CF2Br]-

Conditions
ConditionsYield
With sodium iodide In acetone for 3h; Reflux;98%

65094-22-6Relevant articles and documents

Burton,Flynn

, p. 329 (1977)

Non-metallic compd. Bisphosphonic acid crosslinked layered manufacturing method

-

Paragraph 0128; 0129, (2017/01/02)

PROBLEM TO BE SOLVED: To provide a novel noncrosslinking type layered phosphonic acid metal compound which has high crystallinity and a uniformly introduced multicomponent phosphonic acid and is free of a fluorine atom, and to provide a method for the production of the same.SOLUTION: The method for the production of the noncrosslinking type layered phosphonic acid metal compound includes a reaction step of reacting two or more monophosphonic acids or derivatives thereof having predetermined conditions with a metal source that can generate a hexacoordinated metal atom ion to be a central atom (M) of a metal oxide octahedron upon reaction in the presence of a sulfuric acid catalyst. The noncrosslinking type layered phosphonic acid metal compound obtained by the production method is also provided.

Synthetic and mechanistic aspects of the reactions between bromodifluoromethyltriphenylphosphonium bromide and dibromofluoromethyltriphenylphosphonium bromide and trialkylphosphites

Flynn, Richard M.,Burton, Donald J.,Wiemers, Denise M.

, p. 583 - 589 (2008/12/22)

Bromofluoromethyltriphenylphosphonium bromides react with trialkylphosphites in two distinct ways. Bromodifluoromethyltriphenylphosphonium bromide undergoes a rapid exchange reaction with trialkylphosphites to give the corresponding bromodifluoromethylphosphonates in good to excellent yields. A similar exchange reaction also occurred with an analogous diethoxyphenylphosphonite to give the corresponding ethoxyphenylphosphinate. Mechanistically, the exchange process involves the formation of difluorocarbene via dissociation of the intermediate difluoromethylene ylide, capture of the difluorocarbene by the trialkylphosphite to give [ (RO)3 over(P, +) C over(F2, -) ], which captures bromine followed by dealkylation to the product, bromodifluoromethylphosphonate. The equilibria involved in the multi-step mechanism are all shifted to the phosphonate product by the final dealkylation step. In contrast, the dibromofluoromethyltriphenylphosphonium bromide does not under exchange reactions with trialkylphosphite. The phosphite serves as a halophilic reagent to abstract Br from the dibromofluoromethylphosphonium salt to generate the bromofluoromethylene ylide, which can easily be trapped in situ with aldehydes or ketones to give good yields of the E/Z-bromofluoroalkenes. No dissociation of the bromofluoromethylene ylide was observed.

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