220405-40-3

Basic information

• Product Name: 2,2-Difluoro-1,3-dimethylimidazolidine
• Synonyms: 2,2-Difluoro-1,3-dim;2,2-Difluoro-1,3-Dimethyllimidazolidine;DFI;2,2-DIFLUORO-1,3-DIMETHYLIMIDAZOLIDINE;2,2-difluoro-1,3-dimethyltetrahydroimidazole;Imidazolidine,2,2-difluoro-1,3-dimethyl-;Imidazolidine, 2,2-difluoro-1,3-dimethyl- (9CI);2,2-DIFLUORO-1,3-DIMETHYLIMIDAZOLIDINE (DFI)
• CAS NO: 220405-40-3
• Molecular Formula: C5H10F2N2
• Molecular Weight: 136.14
• Product Categories: Fluorinating Reagents & Building Blocks for Fluorinated Biochemical Compounds;Fluorination;Halogenation;Nucleophilic Fluorinating Reagents;Synthetic Organic Chemistry;AMINETERTIARY;HALIDE;Fluorinating Reagents
• Mol File: 220405-40-3.mol
• Article Data: 6

Chemical Properties

• Boiling Point: 67.107 °C at 760 mmHg
• Flash Point: 40°C
• Appearance: /
• Density: 1.096
• Vapor Pressure: 0.000179mmHg at 25°C
• Refractive Index: 1.442
• Storage Temp.: Refrigerator
• PKA: 0.75±0.40(Predicted)
• CAS DataBase Reference: 2,2-Difluoro-1,3-dimethylimidazolidine(CAS DataBase Reference)
• NIST Chemistry Reference: 2,2-Difluoro-1,3-dimethylimidazolidine(220405-40-3)
• EPA Substance Registry System: 2,2-Difluoro-1,3-dimethylimidazolidine(220405-40-3)

Safety Data

• Hazard Codes: C,F
• Statements: 10-34
• Safety Statements: 16-26-36-45-36/37/39
• RIDADR: 1993
• Hazardous Substances Data: 220405-40-3(Hazardous Substances Data)

Usage

Uses

2,2-Difluoro-1,3-dimethylimidazolidine is a fluorinating agent that has recently been introduced as a potent precursor for the synthesis of p-block element carbene complexes. Also a useful synthetic intermediate in the synthesis of 3-Fluoro-2-methylpropene (F593670).

InChI:InChI=1/C17H36F2N2/c1-5-9-13-20(14-10-6-2)17(18,19)21(15-11-7-3)16-12-8-4/h5-16H2,1-4H3

Synthetic route

2-chloro-1,3-dimethyl imidazolium chloride → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With potassium fluoride In acetonitrile at 80℃; for 17h;	77%

2-chloro-1,3-dimethyl-4,5-dihydro-1H-imidazolium chloride → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
	91%

2-chloro-1,3-dimethylimidazolinium chloride (37091-73-9) → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With triethylamine tris(hydrogen fluoride); triethylamine In dichloromethane Product distribution / selectivity;	91%
With potassium fluoride In 1,3-dimethyl-2-imidazolidinone at 85℃; for 24h;	81%
With potassium fluoride In acetonitrile at 80 - 90℃;

2,2-dichloro-1,3-dimethylimidazolidine (343927-22-0) → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With potassium fluoride In acetonitrile

2-chloro-1,3-dimethylimidazolinium chloride (37091-73-9) → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With triethylamine tris(hydrogen fluoride); triethylamine In dichloromethane Product distribution / selectivity;	91%
With potassium fluoride In 1,3-dimethyl-2-imidazolidinone at 85℃; for 24h;	81%
With potassium fluoride In acetonitrile at 80 - 90℃;

2-chloro-1,3-dimethyl-4,5-dihydro-1H-imidazolium chloride → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
	91%

2-chloro-1,3-dimethyl imidazolium chloride → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With potassium fluoride In acetonitrile at 80℃; for 17h;	77%

2,2-dichloro-1,3-dimethylimidazolidine (343927-22-0) → 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3)

Conditions	Yield
With potassium fluoride In acetonitrile

sodium triflate (2926-30-9) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 2-fluoro-1,3-dimethylimidazolinium trifluoromethanesulfonate (960508-06-9)

Conditions	Yield
In acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;	100%
In [D3]acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;

sodium hexyl sulfate (2832-45-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 2-fluoro-1,3-dimethylimidazolinium hexanesulfonate (960508-14-9)

Conditions	Yield
In acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;	100%
In [D3]acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;

sodium tosylate (657-84-1) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 2-fluoro-1,3-dimethylimidazolinium p-toluenesulfonate (960508-05-8)

Conditions	Yield
In acetonitrile at 0 - 30℃; for 3h; Product distribution / selectivity;	100%
In [D3]acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;

methanesulfonic acid sodium salt (2386-57-4) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 2-fluoro-1,3-dimethylimidazolinium methanesulfonate (960508-04-7)

Conditions	Yield
In acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;	100%
In [D3]acetonitrile at 20 - 30℃; for 3h; Product distribution / selectivity;

methyldichlorophosphane (676-83-5) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C6H13F4N2P (1352439-94-1)

Conditions	Yield
In diethyl ether at -40℃; for 12h; Inert atmosphere;	100%

Dichlorophenylphosphine (644-97-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C11H15F4N2P (1352439-95-2)

Conditions	Yield
In diethyl ether at -40℃; for 12h; Inert atmosphere;	100%

2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C5H10F5N2P (1352439-93-0)

Conditions	Yield
With trifluorophosphane In diethyl ether at -40℃; for 12h; Inert atmosphere;	100%

pentafluoroethyl-difluorophosphane (58734-89-7) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C7H10F9N2P (1550006-97-7)

Conditions	Yield
In diethyl ether at 20℃; for 12h; Schlenk technique; Inert atmosphere;	99%

C4BrF10P (1443773-12-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C9H12F13N2P (1550007-22-1)

Conditions	Yield
In diethyl ether at 20℃; for 12h; Schlenk technique; Inert atmosphere;	98%

N,N,N',N',N'',N''-hexaethylphosphonimidic triamide (74400-91-2) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C17H40N6P(1+)*FH*F(1-)

Conditions	Yield
In dichloromethane at -30 - 20℃;	95%

N,N,N',N'-tetramethyl-N"-(trimethylsilyl)-guanidine (118166-10-2) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C10H22N5(1+)*C3H9F2Si(1-)

Conditions	Yield
In acetonitrile at -30 - 22℃;	95%

tert-butyldimethylsilanol (18173-64-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → tert-butyldimethylfluorosilane (2357-76-8)

Conditions	Yield
In dichloromethane at 20℃; for 1h;	95%

diethoxydiphenylsilane (2553-19-7) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → difluorodiphenylsilane (312-40-3)

Conditions	Yield
In acetonitrile at 20℃; for 1h;	95%

Bis(pentafluoraethyl)-chlorphosphan (35449-89-9) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C9H10F13N2P (1550007-13-0)

Conditions	Yield
In diethyl ether at 20℃; for 12h; Schlenk technique; Inert atmosphere;	95%

1-[(1,1-dimethylethoxy)-carbonyl]-4-hydroxy-2-pyrrolidine carboxylic acid methyl ester (897046-42-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → (2S,4R)-1-tert-butyl 2-methyl 4-fluoropyrrolidine-1,2-dicarboxylate

Conditions	Yield
With potassium hydroxide In toluene	81%

2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 1-Fluoro-octane (463-11-6)

Conditions	Yield
In acetonitrile	80%

trifluoromethyldibromophosphine (2712-92-7) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → C6H10F7N2P (1550006-69-3)

Conditions	Yield
In diethyl ether at 20℃; for 12h; Schlenk technique; Inert atmosphere;	67%

dichloro[4-(4-propylcyclohexyl)phenyl]phosphine (1455481-70-5) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 1,3-dimethylimidazolin-2-ylidene-tetrafluoro[4-(4-propylcyclohexyl)phenyl]phosphorane adduct (1455481-88-5)

Conditions	Yield
In tetrahydrofuran at -40 - 20℃; for 18h; Inert atmosphere;	64%

4-tercbutyl-cyclohexanone (98-53-3) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 1-t-butyl-4-fluoro-3-cyclohexene

Conditions	Yield
In toluene	45%

ethyl 4-oxocyclohexane-1-carboxylate (17159-79-4) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → ethyl 4-fluorocyclohex-3-ene-1-carboxylate

Conditions	Yield
In toluene	21%

2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 1-fluorocyclohexene (694-51-9)

Conditions	Yield
In para-xylene; cyclohexanone	20%

2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) + phenol (108-95-2) → 1,3-dimethyl-2-phenoxyimidazolinium hydrogenfluoride

Methyl 2-deoxy-5-O-(4-phenylbenzoyl)-β-D-threo-pentofuranoside (129468-49-1) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → Biphenyl-4-carboxylic acid (2R,3R,5R)-3-(2-fluoro-1,3-dimethyl-imidazolidin-2-yloxy)-5-methoxy-tetrahydro-furan-2-ylmethyl ester

Conditions	Yield
In toluene at 20℃;

C2F6N(1-)*Rb(1+) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → 1,3-dimethyl-2-fluoroimidazolidinium bis(trifluoromethyl)imide

Conditions	Yield
In acetonitrile at 20℃; for 0.5h;

1-tert-butyl 2-methyl (2S,4R)-4-hydroxy-1,2-pyrrolidinedicarboxylate (74844-91-0) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → N-BOC-3,4-didehydro-(S)-proline methyl ester (74844-93-2) + (S)-1-tert-butyl 2-methyl 2,3-dihydro-1H-pyrrole-1,2-dicarboxylate (83548-46-3) + 1-tert-butyl 2-methyl (2S,4S)-4-fluoropyrrolidine-1,2-dicarboxylate (203866-16-4)

Conditions	Yield
Stage #1: 1-tert-butyl 2-methyl (2S,4R)-4-hydroxy-1,2-pyrrolidinedicarboxylate; 2,2-difluoro-1,3-dimethyl-imidazolidine In toluene at 75℃; for 4h; Stage #2: With potassium hydroxide In water; toluene Product distribution / selectivity;	A 10 %Chromat. B 1.1 %Chromat. C n/a

acetophenone (98-86-2) + 2,2-difluoro-1,3-dimethyl-imidazolidine (220405-40-3) → phenylacetylene (536-74-3)

Conditions	Yield
In acetonitrile

Upstream product

• 343927-22-0 2,2-dichloro-1,3-dimethylimidazolidine 
• 37091-73-9 2-chloro-1,3-dimethylimidazolinium chloride 

Downstream Products

• 312-40-3 difluorodiphenylsilane 
• 74844-93-2 N-BOC-3,4-didehydro-(S)-proline methyl ester 
• 83548-46-3 (S)-1-tert-butyl 2-methyl 2,3-dihydro-1H-pyrrole-1,2-dicarboxylate 
• 203866-16-4 1-tert-butyl 2-methyl (2S,4S)-4-fluoropyrrolidine-1,2-dicarboxylate 
• 536-74-3 phenylacetylene 
• 351-70-2 benzyl trifluoroacetate 
• 372-46-3 fluorocyclohexane 
• 463-11-6 1-Fluoro-octane 
• 350-50-5 benzyl fluoride 
• 455-32-3 benzoyl fluoride 
• 245550-86-1 2-fluoro-1,3-dimethylimidazolinium bromide 
• 350-46-9 4-Fluoronitrobenzene 
• 1006904-66-0 CF₃O^(1-)*C₅H₁₀FN₂⁽¹⁺⁾ 
• 335-05-7 Trifluoromethanesulfonyl fluoride 

Relevant articles and documents

Process for the preparation of guanidinium salts

The present invention relates to a two-step process for the preparation of guanidinium salts of the formula (1), where the substituents R have a meaning indicated in claim, and A? is a sulfonate, alkyl- or arylsulfate, hydrogensulfate, imide, methanide, carboxylate, phosphate, phosphinate, phosphonate, borate, thiocyanate, perchlorate, fluorosilicate or nitrate, and to intermediate compounds from this process.

PROCESS FOR PRODUCING α,α-DIFLUOROAMINE

An industrially practicable process for producing an α,α-difluoroamine, which comprises using specific amounts of hydrogen fluoride and a Lewis base in a halogen-fluorine exchange reaction in which an α,α-dihaloamine is used as a substrate. The process enables the target compound to be obtained in a short time and a high yield. It is easy and has excellent productivity.

Process for producing fluorinated silicon compound

There is disclosed a convenient and efficient process for producing a fluorinated silicon compound which comprises reacting a silicon compound having at least one group selected from the group consisting of a hydroxyl group, an alkoxy group, and an aryloxy group bonded to silicon atom, with a compound represented by the formula (1): wherein R1, R2, R3, and R4may be the same or different, and each represents a substituted or unsubstituted, saturated or unsaturated alkyl group, or a substituted or unsubstituted aryl group; and R1and R2or R3and R4can bond to form a ring having one or more nitrogen atoms or having one or more nitrogen atoms and other hetero atoms; or R1and R3can bond to form a ring having two or more nitrogen atoms or having two or more nitrogen atoms and other hetero atoms, to fluorinate the groups.