3148-73-0

Basic information

• Product Name: Diacetyl hydrazine
• Synonyms: N,N'-DIACETYLHYDRAZINE;N,N-DIACETYLHYDRAZINE;Acetic acid, 2-acetylhydrazide;aceticacid,2-acetylhydrazide;AceticacidN’-acetyl-hydrazide;Hydrazine, 1,2-diacetyl-;N'-Acetylacetohydrazide;NSC 42939
• CAS NO: 3148-73-0
• Molecular Formula: C₄H₈N₂O₂
• Molecular Weight: 116.12
• EINECS: 221-576-1
• Product Categories: Aromatic Hydrazides, Hydrazines, Hydrazones and Oximes;Carbonyl Compounds;Hydrazides;Organic Building Blocks
• Mol File: 3148-73-0.mol
• Article Data: 12

Chemical Properties

• Melting Point: 138-140 °C(lit.)
• Boiling Point: 209 °C15 mm Hg(lit.)
• Flash Point: 209°C/15mm
• Appearance: white crystalline powder
• Density: 1.2829 (rough estimate)
• Vapor Pressure: 0Pa at 25℃
• Refractive Index: 1.4880 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: DMSO (Sparingly), Methanol (Slightly)
• PKA: 11.59±0.23(Predicted)
• Water Solubility: Soluble
• Sensitive: Moisture Sensitive
• BRN: 1754018
• CAS DataBase Reference: Diacetyl hydrazine(CAS DataBase Reference)
• NIST Chemistry Reference: Diacetyl hydrazine(3148-73-0)
• EPA Substance Registry System: Diacetyl hydrazine(3148-73-0)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 20/21/22-36/37/38
• Safety Statements: 26-36-37/39
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 3148-73-0(Hazardous Substances Data)

Usage

Chemical Properties

white crystalline powder

Synthesis Reference(s)

The Journal of Organic Chemistry, 18, p. 872, 1953 DOI: 10.1021/jo50013a016

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C4H6O2.H4N2/c1-3(5)4(2)6;1-2/h1-2H3;1-2H2

Synthetic route

acetic anhydride (108-24-7) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With pyridine; aluminum oxide; hydrazine at 131 - 133℃; for 5h; microwave irradiation;	100%
With hydrazine hydrate
With hydrazine hydrate

acetic anhydride (108-24-7) + acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
In ethanol; water; ethyl acetate at 40 - 45℃; for 4h;	98%

ethyl acetate (141-78-6) + acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
Amano PS Lipase at 25℃; for 48h;	78%

acetic anhydride (108-24-7) + N-(2-acetylamino)phenylglyoxylyl-N'-acetylhydrazine (84966-93-8) → 1-acetyl-1H-indole-2,3-dione (574-17-4) + Diacetylhydrazin (3148-73-0)

Conditions	Yield
In benzene for 5h; Heating;	A 63% B 36%

acetyl chloride (75-36-5) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With pyridine; hydrazine hydrate In tetrahydrofuran at 0℃;	34%

sodium acetate (127-09-3) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With hydrazinium sulfate at 100℃; Behandeln des Produktes mit Essigsaeureanhydrid;

hydrazodicarboxamide (110-21-4) + acetic anhydride (108-24-7) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
at 200℃;

acetic acid (64-19-7) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With hydrazine hydrate

N-acetylacetamide (625-77-4) + acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With pyridine; chloroform

acetic acid hydrazide (1068-57-1) + tetraacetoxysilane (562-90-3) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With benzene

N,N'-dicyclopentylidenehydrazine (20615-04-7) + acetyl chloride (75-36-5) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With diethyl ether

1,3-diphenyl-propen-3-one (614-47-1) → Diacetylhydrazin (3148-73-0) + 1-acetyl-3,5-diphenyl-4,5-dihydro-1H-pyrazole (30693-34-6)

Conditions	Yield
With hydrazine hydrate; acetic acid

acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With trifluoroacetic acid In dimethylsulfoxide-d6
With peracetic acid

bromobenzene (108-86-1) + 1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene (10312-71-7) → Diacetylhydrazin (3148-73-0) + 4'-chloro-4-bromo-biphenyl (23055-77-8) + 2-bromo-4,4’-dichloro-1,1’-biphenyl (179526-95-5) + 3-bromo-4'-chloro-1,1'-biphenyl (164334-69-4) + 1-acetyl-1-p-chlorophenylhydrazine (82408-82-0)

Conditions	Yield
at 131℃; Product distribution; Mechanism; thermolysis, var.: atmosphere : N2, O2, catalyst : m-dinitrobenzene;

triethyl 1,3,5-triazine-2,4,6-tricarboxylate (898-22-6) + acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0) + 1-acetylethoxycarbonylformamidrazone (40253-46-1) + 2-acetyl-5-ethoxycarbonyltetrazole (98189-36-7) + 3,5-diethoxycarbonyl-1,2,4-triazole (91173-78-3)

Conditions	Yield
In ethanol for 2h; Heating; Further byproducts given;	A 0.14 g B 0.57 g C 0.09 g D 0.57 g

triethyl 1,3,5-triazine-2,4,6-tricarboxylate (898-22-6) → Diacetylhydrazin (3148-73-0) + 1-acetylethoxycarbonylformamidrazone (40253-46-1) + 2-acetyl-5-ethoxycarbonyltetrazole (98189-36-7) + 3,5-diethoxycarbonyl-1,2,4-triazole (91173-78-3)

Conditions	Yield
With acetic acid hydrazide In ethanol for 2h; Heating; Further byproducts given;	A 0.14 g B 0.57 g C 0.09 g D 0.57 g

1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene (10312-71-7) → Diacetylhydrazin (3148-73-0) + 1,6-di-p-bromophenyl-3,4-diacetyl-1,5-hexazadiene (79991-24-5) + 1-acetyl-1-p-chlorophenylhydrazine (82408-82-0) + 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
In benzene at 10℃; for 6h; Product distribution; Mechanism; Irradiation; var.: concn., time;

acetic anhydride (108-24-7) → Diacetylhydrazin (3148-73-0) + trisacetylhydrazine (91482-60-9) + tetraacetylhydrazine (3069-07-6)

Conditions	Yield
With hydrazine hydrate at 150℃; for 3h;	A 4 g B 25.6 g C 4.3 g

1-p-chlorophenyl-3,4-diacetyl-1-tetrazene (79991-27-8) → Diacetylhydrazin (3148-73-0) + 4,4'-dichlorobiphenyl (2050-68-2) + 1-acetyl-1-p-chlorophenylhydrazine (82408-82-0) + 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
In benzene at 10℃; for 2h; Product distribution; Mechanism; Irradiation;

ethyl acetate (141-78-6) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With hydrazine hydrate In ethanol for 5h; Heating;	90 % Turnov.

8-fluoro-5-(4-fluorophenyl)-1,3,4,5-tetrahydro-1-benzazepin-2-thione (77796-17-9) + acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0) + 9-fluoro-6-(4-fluorophenyl)-1-methyl-5,6-dihydro-4H-s-triazolo<4,3-a>-1-benzazepine (77796-09-9)

Conditions	Yield
In butan-1-ol for 34h; Heating;

acetic acid hydrazide (1068-57-1) → Diacetylhydrazin (3148-73-0) + 1-acetylethoxycarbonylformamidrazone (40253-46-1) + 2-acetyl-5-ethoxycarbonyltetrazole (98189-36-7) + 3,5-diethoxycarbonyl-1,2,4-triazole (91173-78-3)

Conditions	Yield
With triethyl 1,3,5-triazine-2,4,6-tricarboxylate In ethanol for 2h; Heating; Further byproducts given;	A 0.14 g B 0.57 g C 0.09 g D 0.57 g

1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene (10312-71-7) + chlorobenzene (108-90-7) → Diacetylhydrazin (3148-73-0) + 2,4'-dichlorobiphenyl (34883-43-7) + 3,4'-dichlorobiphenyl (2974-90-5) + 4,4'-dichlorobiphenyl (2050-68-2) + 1-acetyl-1-p-chlorophenylhydrazine (82408-82-0)

Conditions	Yield
at 131℃; Product distribution; Mechanism; thermolysis, var.: photolysis;
at 10℃; for 6h; Product distribution; Mechanism; Irradiation;

1-p-chlorophenyl-3,4-diacetyl-1-tetrazene (79991-27-8) + chlorobenzene (108-90-7) → Diacetylhydrazin (3148-73-0) + 2,4'-dichlorobiphenyl (34883-43-7) + 3,4'-dichlorobiphenyl (2974-90-5) + 4,4'-dichlorobiphenyl (2050-68-2) + 1-acetyl-1-p-chlorophenylhydrazine (82408-82-0)

Conditions	Yield
Product distribution; Mechanism; thermolysis, var.: photolysis, 10 degC;
at 10℃; for 2h; Product distribution; Mechanism; Irradiation;

1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene (10312-71-7) + chlorobenzene (108-90-7) + isopropyl alcohol (67-63-0) → Dimethyl ether (115-10-6) + diacetyl diazene (10465-77-7) + Diacetylhydrazin (3148-73-0) + 2,4'-dichlorobiphenyl (34883-43-7) + 3,4'-dichlorobiphenyl (2974-90-5) + 4,4'-dichlorobiphenyl (2050-68-2)

Conditions	Yield
at 83℃; Product distribution; Mechanism;

...Expand

1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene (10312-71-7) + isopropyl alcohol (67-63-0) → Dimethyl ether (115-10-6) + Diacetylhydrazin (3148-73-0) + chlorobenzene (108-90-7)

Conditions	Yield
at 83℃; Product distribution; Mechanism; thermolysis;

acetamide (60-35-5) → Diacetylhydrazin (3148-73-0)

Conditions	Yield
With fluorine; sodium fluoride In [D3]acetonitrile at -40℃; for 0.166667h;

Diacetylhydrazin (3148-73-0) → 2,5-dimethyl-1,3,4-thiadiazole (27464-82-0)

Conditions	Yield
With Lawessons reagent In xylene at 140℃; for 3.5h;	100%
With tetraphosphorus decasulfide In xylene for 1h; Heating;
With tetraphosphorus decasulfide

Diacetylhydrazin (3148-73-0) + N,N-bis[chloro(phenyl)phosphino]methylamine (49774-14-3) → 1,2-diacetyl-4-methyl-3,5-diphenyl-1,2,4-triaza-3,5-diphospholidine

Conditions	Yield
With triethylamine In N,N-dimethyl-formamide at 75℃;	97%

Diacetylhydrazin (3148-73-0) → 1,1'-(diazene-1,2-diyl)diethanone

Conditions	Yield
With hydrogenchloride; dihydrogen peroxide; acetic acid; titanium(III) chloride; hydrogen bromide In methanol at 20℃;	91%
With lead(IV) acetate In dichloromethane at 25℃; for 2h;	36%

ammonium hexafluorophosphate + cis-bis-(2,2′-bipyridine) dichlororuthenium(II) dihydrate + Diacetylhydrazin (3148-73-0) → (μ-1,2-diacetylhydrazido(2-))bis(bis(2,2'-bipyridine)ruthenium(II)) bis(hexafluorophosphate)

Conditions	Yield
With sodium hydroxide In ethanol; water heating cis-Ru(bpy)2Cl2*2H2O with 1,2-diacetylhydrazine and NaOH in H2O/EtOH (reflux, 24 h), adding NH4PF6 in H2O, pptn.; drying (vac.), dissolving (acetone), adding Et2O (pptn.), drying (vac.); elem. anal.;	91%
With NaOH In ethanol; water Ar atmosphere; refluxing Ru-complex, hydrazine derivative and NaOH in H2O/EtOH=5:1 (24 h), cooling to room temp., addn. of aq. NH4PF6, (pptn.); drying (vac.), dissolving (acetone), pptn. (Et2O), drying (vac.);	91%

Diacetylhydrazin (3148-73-0) + 2-chloro-ethanol (107-07-3) → 1,2-bis(2'-hydroxyethyl)-1,2-diacetylhydrazine (62562-66-7)

Conditions	Yield
With sodium hydroxide for 24h; Ambient temperature;	85%

Cyclohexyl isocyanide (931-53-3) + Diacetylhydrazin (3148-73-0) + dimethyl acetylenedicarboxylate (762-42-5) → 1,2-diacetyl-5-cyclohexylamino-2,3-dihydro-1H-pyrazole-3,4-dicarboxylic acid dimethyl ester

Conditions	Yield
In acetone at 20℃; for 24h;	85%

Diacetylhydrazin (3148-73-0) + tert-butylisonitrile (119072-55-8, 7188-38-7) + dimethyl acetylenedicarboxylate (762-42-5) → 1,2-diacetyl-5-tert-butylamino-2,3-dihydro-1H-pyrazole-3,4-dicarboxylic acid dimethyl ester

Conditions	Yield
In acetone at 20℃; for 24h;	84%

1,3-bis-(2,6-diisopropyl-phenyl)-6-methyl-4-methylene-1,2,3,4-tetrahydro-[1,3,2]diazasiline (907590-97-0) + Diacetylhydrazin (3148-73-0) → C33H48N4O2Si (1355360-86-9)

Conditions	Yield
In hexane at 20℃; for 12h; Inert atmosphere;	84%

Diacetylhydrazin (3148-73-0) + Di-tert-butyl acetylenedicarboxylate (66086-33-7) + Tri(p-tolyl)phosphine (1038-95-5) → di-tert-butyl 2-(N,N'-diacetylhydrazino)-3-(tri-p-tolylphosphanylidene)butanedioate

Conditions	Yield
In acetone at -10℃;	83%

Diacetylhydrazin (3148-73-0) + dimethyl acetylenedicarboxylate (762-42-5) + Tri(p-tolyl)phosphine (1038-95-5) → dimethyl 2-(N,N'-diacetylhydrazino)-3-(tri-p-tolylphosphanylidene)butanedioate

Conditions	Yield
In acetone at -10℃;	80%

Diacetylhydrazin (3148-73-0) → 2,5-dimethyl-1,3,4-oxadiazole (13148-65-7)

Conditions	Yield
With methanesulfonic acid; pyrophosphoric acid at 70℃; for 4h;	78%
With thionyl chloride In 1,4-dioxane Heating;
With acetic anhydride Heating;

chloro-trimethyl-silane (75-77-4) + Diacetylhydrazin (3148-73-0) → bis trimethylsilyl diacetylhydrazine (124551-47-9, 126810-79-5)

Conditions	Yield
With triethylamine for 10h; Heating;	78%

Diacetylhydrazin (3148-73-0) + dimethyl acetylenedicarboxylate (762-42-5) + triphenylphosphine (603-35-0) → dimethyl 2-(N,N'-diacetylhydrazino)-3-(triphenylphosphanylidene)butanedioate

Conditions	Yield
In acetone at -10℃;	77%

ammonium hexafluorophosphate + cis-[bis(2,2'-bipyridine)dichloridoosmium(II)] (79982-56-2) + Diacetylhydrazin (3148-73-0) → (μ-1,2-diacetylhydrazido(2-))bis(bis(2,2'-bipyridine)osmium(II)) bis(hexafluorophosphate)

Conditions	Yield
With sodium hydroxide In ethanol; water heating mixt. of cis-Os(bpy)2Cl2, 1,2-diacetylhydrazine and NaOH in EtOH/H2O (reflux, 48 h), cooling, adding NH4PF6 in H2O, pptn.; drying, recrystn. (acetone/Et2O 1:4), chromy. (alumina, acetone); elem. anal.;	77%

Diacetylhydrazin (3148-73-0) + tert-butylisonitrile (119072-55-8, 7188-38-7) + acetylenedicarboxylic acid diethyl ester (762-21-0) → 1,2-diacetyl-5-tert-butylamino-2,3-dihydro-1H-pyrazole-3,4-dicarboxylic acid diethyl ester

Conditions	Yield
In acetone at 20℃; for 24h;	75%

Cyclohexyl isocyanide (931-53-3) + Diacetylhydrazin (3148-73-0) + acetylenedicarboxylic acid diethyl ester (762-21-0) → 1,2-diacetyl-5-cyclohexylamino-2,3-dihydro-1H-pyrazole-3,4-dicarboxylic acid diethyl ester

Conditions	Yield
In acetone at 20℃; for 24h;	72%

Diacetylhydrazin (3148-73-0) + Di-tert-butyl acetylenedicarboxylate (66086-33-7) + triphenylphosphine (603-35-0) → di-tert-butyl 2-(N,N'-diacetylhydrazino)-3-(triphenylphosphanylidene)butanedioate

Conditions	Yield
In acetone at -10℃;	67%

Diacetylhydrazin (3148-73-0) + p-chlorobenzenediazonium chloride (2028-74-2) → 1-p-chlorophenyl-3,4-diacetyl-1-tetrazene (79991-27-8)

Conditions	Yield
With sodium carbonate In diethyl ether at 0℃;	65%

cis-dichlorobis(trimethylphosphine)platinum(II) (19471-47-7, 15630-86-1, 21545-76-6) + Diacetylhydrazin (3148-73-0) → (P(CH3)3)2Pt(CH3CON2COCH3)

Conditions	Yield
With NaHCO3 In ethanol (Ar); refluxing (4 h); solvent removal (vac.), dissolving (benzene), pptn. on hexane addn.; elem. anal.;	65%

chloro-trimethyl-silane (75-77-4) + Diacetylhydrazin (3148-73-0) → C10H24N2O2Si2

Conditions	Yield
With triethylamine for 10h; Heating;	60%

Diacetylhydrazin (3148-73-0) + 3-oxa-1,5-dichloropentane (111-44-4) → N,N'-diacetyl[1,4,5]-oxadiazepane (83598-13-4)

Conditions	Yield
With potassium hydroxide; potassium carbonate; tetramethlyammonium chloride In dimethyl sulfoxide at 80 - 85℃; under 15.0015 - 30.003 Torr; for 5h;	52.3%

Diacetylhydrazin (3148-73-0) + di-tert-butyl dicarbonate (24424-99-5) → N,N'-diacetyl-hydrazinecarboxylic acid tert-butyl ester

Conditions	Yield
With dmap In acetonitrile at 20℃; for 17h;	51%

NH-pyrazole (288-13-1) + bis(acetylacetonate)oxovanadium (3153-26-2) + Diacetylhydrazin (3148-73-0) + oxygen (80937-33-3) → [(pyrazole)O2V(μ-N.N'-bis(diacetyl)hydrazine(-2H))VO2(pyrazole)]

Conditions	Yield
In water; acetonitrile aq. soln. of H2diah added to MeCN soln. of Himdz and V compd. (1:2:2 molaer ratio), mixt. refluxed for 6 h; filtered, crystd. on storage at 5°c for 7 d, ppt. filtered off, washed (MeCN), dried in air, elem. anal.;	48%

3,5-dimethyl-1H-pyrazole (67-51-6) + bis(acetylacetonate)oxovanadium (3153-26-2) + Diacetylhydrazin (3148-73-0) + oxygen (80937-33-3) → [(3,5-dimethylpyrazole)O2V(μ-N.N'-bis(diacetyl)hydrazine(-2H))VO2(3,5-dimethylpyrazole)]

Conditions	Yield
In water; acetonitrile aq. soln. of H2diah added to MeCN soln. of Himdz and V compd. (1:2:2 molaer ratio), mixt. refluxed for 6 h; filtered, crystd. on storage at 5°c for 7 d, ppt. filtered off, washed (MeCN), dried in air, elem. anal.;	47%

1H-imidazole (288-32-4) + bis(acetylacetonate)oxovanadium (3153-26-2) + Diacetylhydrazin (3148-73-0) + water (7732-18-5) + oxygen (80937-33-3) → [(imidazole)O2V(μ-N.N'-bis(diacetyl)hydrazine(-2H))VO2(imidazole)]*2H2O

Conditions	Yield
In water; acetonitrile aq. soln. of H2diah added to MeCN soln. of Himdz and V compd. (1:2:2 molaer ratio), mixt. refluxed for 6 h; filtered, crystd. on storage at 5°c for 7 d, ppt. filtered off, washed (MeCN), dried in air, elem. anal.;	41%

Upstream product

• 110-21-4 hydrazodicarboxamide 
• 108-24-7 acetic anhydride 
• 1068-57-1 acetic acid hydrazide 
• 64-19-7 acetic acid 
• 108-86-1 bromobenzene 
• 10312-71-7 1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene 
• 898-22-6 triethyl 1,3,5-triazine-2,4,6-tricarboxylate 
• 79991-27-8 1-p-chlorophenyl-3,4-diacetyl-1-tetrazene 
• 141-78-6 ethyl acetate 
• 108-90-7 chlorobenzene 
• 67-63-0 isopropyl alcohol 
• 75-36-5 acetyl chloride 
• 84966-93-8 N-(2-acetylamino)phenylglyoxylyl-N'-acetylhydrazine 
• 77796-17-9 8-fluoro-5-(4-fluorophenyl)-1,3,4,5-tetrahydro-1-benzazepin-2-thione 

Downstream Products

• 79991-27-8 1-p-chlorophenyl-3,4-diacetyl-1-tetrazene 
• 13148-65-7 2,5-dimethyl-1,3,4-oxadiazole 
• 4046-03-1 2-methyl-5-phenyl-[1,3,4]oxadiazole 
• 40746-64-3 5-methyl-1-(3-nitrophenyl)tetrazole 
• 60-35-5 acetamide 
• 14213-16-2 5-methyl-1-phenyl-1H-tetrazole 
• 431-03-8 dimethylglyoxal 
• 1355360-86-9 C₃₃H₄₈N₄O₂Si 
• 72470-51-0 1-(2'-carboxyphenyl)-5-methyltetrazole 
• 16114-05-9 N,N'-bis(dimethylaminomethylene)hydrazine 
• 59105-37-2 3-acetyl-5-methyl-3H-[1,2,3,4]oxathiadiazole 2-oxide 
• 27464-82-0 2,5-dimethyl-1,3,4-thiadiazole 
• 1615-80-1 N,N'-diethylhydrazine 

Relevant articles and documents

15N and 13C NMR Study of Acylated Hydrazines. The Instability of Trifluoroacethydrazide in the Solid State

Trifluoroacethydrazide is unstable even in the solid state with respect to hydrazonium N,N'-ditrifluoroacetyl hydrazinate, as shown by 15N and 13C NMR spectroscopy.The 1H, 13C and 15N NMR data and rotamer distributions of formyl-, acet- and trifluoroacet-hydrazide and of N,N'-diformyl-, N,N'-diacetyl- and N,N'-ditrifluoroacetylhydrazine are reported and compared with the results of earlier investigations.A conformational dependence is observed for 1J(NH) and 2J(NH) in the formylhydrazides and of 1J(NH), 2J(NH) and 3J(NH) in the N,N'-diformylhydrazines.The conformational dependence of 2J(CH) in formamide, reported in the literature, however, could not be confirmed.

Synthesis of α-aminocarbonyl compounds via hetero dielsalder reaction

A synthetic route to α-aminoketone derivatives via a hetero DielsAlder reaction is described. Diacylhydrazine was oxidized by tert-butyl hypochlorite in the presence of pyridine. After evaporation, the hetero DielsAlder reaction with diene was carried out without isolation of the azodicarbonyl compound. Quantitative hetero DielsAlder reaction was possible with 1 equivalent of diene when Hf(OTf)4 or AgOTf was used as the catalyst. The NN bond of the product was cleaved by SmI2-reduction in the presence of tert-BuOH in THF. Further, ozonolysis of the C=C double bond afforded the α-aminoketone derivative in excellent yield.

A New Preparation of gem-bis(Difluoramino)-alkanes via Direct Fluorination of Geminal Bisacetamides

A fundamentally new preparation of internal and terminal gem-bis-(diflouramino)alkanes has been demonstrated by the direct flourination of corresponding gem-bisacetamides, specifically, 1,1-bisacetamidocyclohexane and 1,1-bisacetamidopropane, leading to 1,1-bis(diflouramino)cyclohexane and 1,1-bis(diflouramino)-propane, respectively.