100-63-0

Basic information

• Product Name: Phenylhydrazine
• Synonyms: 1-Hydrazinobenzene;Phenyl hydrazide;Phenylhydrazine,95%;Phenylhydrazine ,98%;Phenylhydrazine, extra pure;PHENYLHYDRAZINE GR FOR ANALYSIS;Phenylhydrazine, >=95.0% (GC);1-Phenylhydrazine
• CAS NO: 100-63-0
• Molecular Formula: C₆H₈N₂
• Molecular Weight: 108.14
• EINECS: 202-873-5
• Product Categories: Phenylhydrazine;HydrazinesSpectroscopy;UV/Vis Reagents;UV/Visible (UV/VIS) Spectroscopy;Organic Building Blocks;ChromophoresOrganic Building Blocks;Glycan Labeling;Glycan Labeling and Analysis;Hydrazines;Nitrogen Compounds;Amines;Aromatics;Intermediates & Fine Chemicals;Pharmaceuticals;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks;fine chemicals
• Mol File: 100-63-0.mol
• Article Data: 65

Chemical Properties

• Melting Point: 19 °C
• Boiling Point: 238-241 °C(lit.)
• Flash Point: 192 °F
• Appearance: White to slightly blue or light beige/Powder
• Density: 1.099 g/mL at 25 °C(lit.)
• Vapor Density: 4.3 (vs air)
• Vapor Pressure: <0.1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.607(lit.)
• Storage Temp.: Store at RT.
• Solubility: Soluble in dilute acids.
• PKA: 8.79(at 15℃)
• Explosive Limit: 1.1%(V)
• Water Solubility: 145 g/L (20 ºC)
• Sensitive: Air & Light Sensitive
• Stability: Stable, but may decompose in sunlight. May be air or light sensitive. Incompatible with strong oxidizing agents, metal oxides.
• Merck: 14,7293
• BRN: 606080
• CAS DataBase Reference: Phenylhydrazine(CAS DataBase Reference)
• NIST Chemistry Reference: Phenylhydrazine(100-63-0)
• EPA Substance Registry System: Phenylhydrazine(100-63-0)

Safety Data

• Hazard Codes: T,N
• Statements: 45-23/24/25-36/38-43-48/23/24/25-50-68
• Safety Statements: 53-45-61
• RIDADR: UN 2572 6.1/PG 2
• WGK Germany: 3
• RTECS: MV8925000
• F: 8-10-23
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 100-63-0(Hazardous Substances Data)

Usage

Chemical Description

Phenylhydrazine and benzoylhydrazine are both hydrazine derivatives that contain a phenyl and benzoyl group, respectively.

Hydrazine derivative

Phenylhydrazine is also known as the hydrazinobenzene. It was first successfully synthesized by the German organic chemist Hermann-Emil-Fischer in 1875 and is the first synthesized hydrazine derivatives. At room temperature, it is a pale yellow crystalline or oily liquid while at low temperature it appears as monoclinic prismatic crystals. It can be easily subject to oxidization in the air and exhibit dark brown or dark red. Phenylhydrazine is one of the hydrazine derivatives and is often abbreviated as PhNHNH2. It is slightly soluble in water and alkali solution and can be dissolved in dilute acid. It is miscible with ethanol, ethyl ether, chloroform and benzene. Common method of its preparation is through the reaction between aniline and sodium nitrite under the action of hydrochloric acid for generation of diazonium salt which is then reduced by sulfite/sodium reduction for obtaining it. Acid precipitation can generate phenylhydrazine hydrochloride with neutralization generating phenylhydrazine. Phenylhydrazine can be applied to making dyes, drugs, and being used as developer. It is also an important reagent for identification of carbonyl group and can be used for identifying aldehydes, ketones and carbohydrates. It can react with benzaldehyde to generate phenylhydrazine. We can use the hydrazone generated through phenylhydrazine or 2, 4-dinitrophenylhydrazine to identify aldehydes and ketones, It can trigger Fischer indole synthesis upon reaction with aldehydes and ketones (first found by the Emil Hermann Fischer in 1883, the reaction is using phenylhydrazine and aldehyde, ketone for heating and rearrangement under acid-catalysis for the elimination of one molecule of ammonia to give 2-or 3-substituted indole.) to give indole ring-class compound.

Hermann Emil Fischer

Phenylhydrazine (Hydrazinobenzene) is the chemical compound characterized by Hermann Emil Fischer in 1895. Fischer is a German organic chemist. He used phenylhydrazine to react with carbohydrate and generate hydrazone and osazone and form a crystalline compound which is easy for purification. Then it is decomposed into pure sugar. This is a powerful means for studying carbohydrate structures and synthesis of a variety of sugars and enables the theoretic clarification of the structure of glucose and summarizing of the general stereoisomerism phenomenon of saccharides and further using of Fischer projection for describing it. He has also demonstrated that the caffeine, theophylline, uric acid all belongs to purine derivatives and also had successfully synthesized purine. He also had opened up the study of proteins and had demonstrated that amino acids forms polypeptide via peptide bond and successfully synthesized polypeptides. In 1902, Fischer, because of the synthesis of purine and carbohydrate, was awarded for the Nobel Prize in Chemistry. The above information is edited by the lookchem of Dai Xiongfeng.

Phenylhydrazine: preparation and application

Phenylhydrazine is the first synthetic hydrazine derivatives which can often be used as intermediates of organic dyes, pharmaceuticals and pesticide. It can also be used as organic intermediates for synthesis of pyrazoline, triazole, and indole; It can also be used as dye intermediates like disazo dye intermediates such as 1-phenyl-3-methyl-5-pyrazolone and so on; It can also be used as pharmaceutical intermediates for preparation of antipyretic, analgesic, anti-inflammatory drugs such as antipyrine and aminopyrine, etc; it can also be used as photography drugs (photosensitive dye); phenylhydrazine is also the raw material for the production of pesticides "imputed phosphorus"; phenylhydrazine is also an important kind of carbonyl group identification reagents used for identifying aldehydes, ketones and carbohydrates. Phenylhydrazine is toxic. After inhalation, due to hemolysis, it can cause anemia and headache and can even cause jaundice in severe cases. It can also have stimulating effect on the eyes such as causing corneal disorders. Rat-oral LD50:188 mg/kg. Workplace: maximum allowable concentration: 0.44mg/m3. Lab often uses aniline as raw materials for reaction with sodium nitrite in hydrochloric acid for generating diazonium salt and then reacted with sulfur dioxide and sulfurous acid for reduction to produce phenylhydrazine sodium sulfonate and further salting via hydrochloric acid to form phenylhydrazine hydrochloride. After neutralization and deacidification, we can obtain phenylhydrazine.

Chemical Properties

Different sources of media describe the Chemical Properties of 100-63-0 differently. You can refer to the following data:
1. Phenylhydrazine is pale yellow oily liquid with the melting point being 19.8 ℃ and boiling point being 173.5 ℃/13.33kPa, n20D being 1.608 and the relative density being 1.0978 (20 ℃). It is slightly soluble in water and petroleum ether and soluble in alcohol, ether, chloroform and benzene. It can be evaporated together with steam. It is also easily to get dark in the air. Phenylhydrazine hydrochloride [59-88-1] is solid with the m.p. being 250~254 ℃ (decomposition).
2. Phenylhydrazine is a colorless to pale yellow liquid or solid with a weak aromatic odor. It is soluble in water (values ranging from 145 to 837 g/litre at 24 °C have been reported) and is miscible with alcohol, ether, chloroform, benzene, and acetone. The conversion factor for phenylhydrazine is 1 ppm = 4.5 mg/m3 (at 20 °C, 101 kPa).

Uses

Different sources of media describe the Uses of 100-63-0 differently. You can refer to the following data:
1. In the field of pesticide production, phenylhydrazine can be used for synthesizing the intermediate 1-phenyl-semicarbazide of the organophosphorus pesticides, triazophos as well as the intermediate 1-phenyl-3, 6-hydroxy pyridazine of pyridaphenthione. It is also the intermediates of the novel bactericidal varieties, famoxadone and fenamidone. In addition, hydrazine benzene, as a raw material for organic synthesis, can also be used as the intermediates of dye and pharmaceutical industry as well as being used as an analytical reagent. The product is the intermediate of dye, pharmaceuticals and pesticides. It can be used for the production of Naphthol AS-G, drugs such as antipyrine and so on. Dissolving the phenylhydrazine in 95% ethanol and following by addition of benzaldehyde and reflux for 1 h can obtain the phenylhydrazone. Phenylhydrazone can also be used as the intermediate of organic synthesis. Phenylhydrazine is also used as an analytical reagent. As a weak base, it can be used to precipitate lead, chromium and other trivalent, tetravalent element in the form of hydroxide. It can also be used for photometric determination of aluminum, chromium, copper, molybdenum, titanium, and zirconium. It can also be used for verification of gold, iridium, molybdenum, palladium, platinum, and silver. It can be used as the reducing agent for colorimetric assay of phosphorus acid. It can also react with aldehydes, ketones and sugars to get phenylhydrazone with different melting points according which we will be able to identify these substances.
2. Phenylhydrazine, as hydrochloride solution plus sodium acetate, reacts with polyhydroxy aldehydes or ketones yielding osazones or diphenylhydrazones, yellow solids, of definite melting point and utilized in identification of sugars, e.g., phenyl-d-glucosazone, CH2OH (CHOH)3C: (NNHC6H5)CH:(NNHC6H5) plus aniline C6H5NH2 plus NH3.
3. Phenylhydrazine is used in the manufactureof dyes and pharmaceuticals; as a stabilizerfor explosive; as a reagent for aldehydes,ketones, and sugars in chemical analysis; andin organic synthesis.
4. An aryl hydrazine used in the preparation of various dyes and pharmaceutical compounds. It is used in the investigation of oligosaccharides as well as the structure of photosystem II.

Production method

It can be produced from aniline which undergoes diazotization, reduction, acid precipitation to obtain phenylhydrazine hydrochloride and then further neutralization to obtain phenylhydrazine. The preparation method is based on aniline which successively undergoes diazotization, reduction, acid precipitation, and neutralization to derive it. Diazotization: add a certain amount of water, 30% hydrochloric acid and aniline to the reaction pot, cooled to 2 ℃, control the temperature at around 0~5 ℃ and add drop wise of solution of sodium nitrite to until the starch iodide test solution turns blue, stir for 30 mins for completion of the reaction and obtain the diazonium solution. Reduction: add water, sodium bisulfite and 30% alkaline solution to the reduction kettle, heated to 80 ℃, maintain the temperature in 80~85 ℃ and pH = 6.2~6.7, within 20min trickle add the above diazo solution, stirring was continued for 1.5 h, then add zinc powder, diatomaceous earth, stirred filtrate with the filtrate suck into the acid precipitation tank. Acid precipitation: to the above filtrate add 30% hydrochloric for acid precipitation at 70 ℃, the temperature is maintained in 85~90 ℃, stir for 10min and cool to below 20 ℃, suck, filtration to yield phenylhydrazine hydrochloride. Neutralization: add the alkaline solution to the reaction pot, stir and simultaneously add the above phenylhydrazine hydrochloride and an appropriate amount of water, heated to 50 ℃, stirred at 50~60 ℃ for 1 h, allowed to stand for more than 8h, separate out the lower aqueous solution, It was the top oil that was phenylhydrazine with the content of about 80% and the total yield of 83.5%.

Mutagenicity and Toxicity of Carcinogenic

Phenylhydrazine is toxic by single exposure via the oral route (LD50 80–188 mg/kg body weight) and is expected to be toxic by the inhalation and dermal routes (data from these routes of exposure are less clear). Phenylhydrazine has potential for skin and eye irritation,and there is evidence that it has skin-sensitizing properties in humans. Exposure to phenylhydrazine may cause damage to red blood cells, potentially resulting in anaemia and consequential secondary involvement of other tissues, such as the spleen and liver. Phenylhydrazine is mutagenic in vitro, and there is some evidence to indicate that it may express genotoxic activity in vivo. The substance is clearly carcinogenic in mice following oral dosing, inducing tumours of the vascular system. The mechanism for tumour formation is unclear, but a genotoxic component cannot be excluded. Hence, it is not considered possible to reliably identify a level of exposure at which there will be no risk of carcinogenic or genotoxic effects.

environmental effects

Phenylhydrazine is degraded photochemically and autoxidizes in water. It is readily biodegradable, and this is expected to be the major route of breakdown in the environment. There is minimal sorption to particulates. Phenylhydrazine is toxic to aquatic organisms, with the lowest reported no-observed-effect concentration (NOEC) in standard acute fish tests at 0.01 mg/litre; fish are generally more sensitive than either daphnids or bacteria. A NOEC of 0.49 :g/litre has been reported for embryo-larval stages of the zebra fish (Brachydanio rerio).

Flammable and hazard characteristics

it is combustible upon fire with heating emitting toxic nitrogen compound gas

Storage characteristics

Treasury: ventilation, low-temperature and dry; store it separately from oxidants, acids and food additives

Extinguishing agent

water, spray, foam, CO2, sand

Professional Standards

TLV-TWA 0.1 PPM; TWA 5 PPM (22 mg/cubic meter); STEL 2 mg/m3

Physical properties

Yellow monoclinic crystals with a faint, aromatic odor. Turns red-brown on exposure to air.

Definition

ChEBI: A phenylhydrazine that is the monophenyl derivative of hydrazine.

Synthesis Reference(s)

Synthesis, p. 738, 1975 DOI: 10.1055/s-1975-23917

General Description

Pale yellow crystals. Melting point 66°F. Becomes an oily liquid. Toxic by ingestion, inhalation and skin absorption. Flash point 192°F. Autoignition temperature 345°F. Soluble in alcohol.

Air & Water Reactions

When exposed to air becomes red-brown. Slightly denser than water and slightly soluble in water.

Reactivity Profile

Phenylhydrazine may ignite spontaneously when in contact with oxidants such as hydrogen peroxide or nitric acid, oxides of iron or copper, or manganese, lead, copper or their alloys. Will not polymerize [USCG, 1999].

Health Hazard

Phenylhydrazine is a moderate to highlytoxic compound and a carcinogen. Acutetoxic symptoms include hematuria, changesin liver and kidney, vomiting, convulsions,and respiratory arrest. Additional symptomsare lowering of body temperature and fallin blood pressure. Chronic exposure to thiscompound caused hemolytic anemia andsignificant body weight loss in rats. Anoral administration of 175 mg/kg was lethalto mice. An oral LD50 value in rat is188 mg/kgPhenylhydrazine caused adverse repro ductive effect when dosed intraperitoneallyin pregnant mice. It caused jaundice, anemia,and behavioral deficit in offspring Oral or subcutaneous administration ofphenylhydrazine or its hydrochloride produced lung and liver tumors in experimental animals. ACGIH lists this compoundas a suspected human carcinogen. The evidence of carcinogenicity of this compoundin human is inadequate.

Fire Hazard

Combustible liquid; flash point (closed cup) 89°C (192°F). It reacts with lead dioxide and strong oxidizing compounds vigorous to violently.

Safety Profile

Confirmed carcinogen with experimental carcinogenic data. Poison by ingestion, subcutaneous, and intravenous routes experimental reproductive effects Mutation data reported. Ingestion or subcutaneous injection can cause hemolysis of red blood cells. Other effects are damage to the spleen, liver, kidneys, and bone marrow. The most common effect of occupational exposure is the development of dermatitis, which, in sensitized persons, may be quite severe. Systemic effects include anemia and general weakness, gastrointestinal dsturbances, and injury to the kidneys. Flammable when exposed to heat, flame, or oxidizers. To fight fire, use alcohol foam. Violent reaction with 2phenylamino-3-phenyloxazirane. Reacts with perchloryl fluoride to form an explosive product. Vigorous reaction with lead(Ⅳ) oxide. Used as a chemical reagent, in organic synthesis, and in the manufacture of dyes and drugs. Dangerous; when heated to decomposition it emits highly toxic fumes of NOx; can react with oxidizing materials

Potential Exposure

Phenylhydrazine is a widely used reagent in conjunction with sugars, aldehydes, and ketones. In addition, to its use in the synthesis of dyes; pharmaceuticals, such as antipyrin; cryogenin, and pyramidone; and other organic chemicals. The hydrochloride salt is used in the treatment of polycythemia vera.

Carcinogenicity

Mice given 1mg phenylhydrazine orally each day, 7 days/week for 42 weeks had an increased incidence of total lung tumors. The incidence of malignant tumors also increased. In another study, mice administered 0.01% of the hydrochloride salt in drinking water (average of 0.63–0.81 mg/day) over their lifetimes had an increased incidence of blood vessel tumors. In contrast, mice given phenylhydrazine orally 5 days/week for 40 weeks at doses of 0.5 mg during the first 5 weeks and 0.25 mg thereafter failed to develop tumors.Higher doses could not be tested because of the marked anemia encountered. No leukemias occurred in mice treated with phenylhydrazine, and pulmonary tumors were infrequent . Oral administration or intraperitoneal injection (eight doses, each of 2.9 mg) of phenylhydrazine hydrochloride in mice failed to increase either pulmonary tumors or leukemia. The carcinogenic activity of hydrazine itself has been closely linked to its toxicity, that is, its irritant effect. The mechanism of action, it is postulated, is indirect alkylation of DNA, which is also closely connected to the toxic end point.

Shipping

UN2572 Phenylhydrazine, Hazard Class: 6.1; Labels: 6.1-Poisonous materials.

Purification Methods

Purify phenylhydrazine by chromatography, then crystallise it from pet ether (b 60-80o)/*benzene. Store it in the dark under N2 as it turns yellow, then red, on exposure to air. It is best stored as the hydrochloride salt; see below. [Coleman Org Synth Coll Vol I 442 1941, Shaw & Stratton J Chem Soc 5004 1962, Beilstein 15 IV 50.]

Incompatibilities

Phenylhydrazine is very reactive with carbonyl compounds, strong oxidizers; strong bases; alkali metals; ammonia, lead dioxide (violent). Attacks copper salts, nickel, and chromates.

Waste Disposal

Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device.

InChI:InChI=1/C6H5.H3N2/c1-2-4-6-5-3-1;1-2/h1-6H;1-2H2

Synthetic route

benzene diazonium chloride (100-34-5) → phenylhydrazine (100-63-0)

Conditions	Yield
With palladium on activated charcoal; hydrogen at 30℃; under 3000.3 Torr; for 2h; Temperature; Pressure; Reagent/catalyst; Autoclave;	94%
With hydrogenchloride; potassium chloride Electrolysis;
With hydrogenchloride; tin(ll) chloride

aniline (62-53-3) → phenylhydrazine (100-63-0)

Conditions	Yield
With ammonium hydrogen sulfite; ammonium nitrite; ammonium bisulfite; sulfuric acid at 40 - 70℃; for 4h; pH=3;	87.5%
Stage #1: aniline With hydrogenchloride; sodium nitrite In water at 65℃; pH=2.5; Stage #2: With ammonium hydrogen sulfite In water at 8 - 70℃; for 1.75h; Temperature; pH-value; Further stages;	84%
Stage #1: aniline With hydrogenchloride; sodium nitrite In water for 2h; Stage #2: With hydrogenchloride; sodium sulfite In water at 0 - 100℃; for 4h;	78.74%

iodobenzene (591-50-4) → phenylhydrazine (100-63-0)

Conditions	Yield
With potassium phosphate; copper(l) iodide; Oxalsaeure-bis-<β-benzoylhydrazid>; hydrazine hydrate In dimethyl sulfoxide at 20℃; for 12h;	83%
With hydrazine hydrate for 3h; Reflux;
With potassium phosphate; copper(l) iodide; hydrazine hydrate at 120℃; for 6h; Sealed tube; Inert atmosphere;
Stage #1: iodobenzene With oxalic acid hydrazide; potassium phosphate; cetyltrimethylammonim bromide; 2,5-hexanedione; copper(I) bromide In water at 110℃; for 0.166667h; Sealed tube; Stage #2: With hydrazine hydrate In water at 110℃; for 1h; Sealed tube;	68 %Chromat.

benzenediazonium tetrafluoroborate (369-57-3) → phenylhydrazine (100-63-0)

Conditions	Yield
With nickel dichloride; zinc In tetrahydrofuran Reduction;	80%
Multi-step reaction with 2 steps 1: water; tetrahydrofuran / 0 - 20 °C 2: sulfuric acid / water; isopropyl alcohol / 6 h / Reflux View Scheme

C24H22N2P(1+)*BF4(1-) → phenylhydrazine (100-63-0)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol for 6h; Reflux;	79%

triphenyl-(N'-phenyl-hydrazino)-phosphonium; chloride → phenylhydrazine (100-63-0)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol for 6h; Reflux;	75%

C24H22N2P(1+)*C2H3O2(1-) → phenylhydrazine (100-63-0)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol for 6h; Reflux;	70%

4-tert-butyl-1,3-diphenyl-5-(E)-styryl-1,2,4-triazoline (90331-10-5) → N-t-butylbenzamide (5894-65-5) + 3-phenyl-propenal (104-55-2) + phenylhydrazine (100-63-0) + (E)-1,3-diphenyl-5-styryl-1H-1,2,4-triazole

Conditions	Yield
With hydrogenchloride In ethanol for 4h; Ambient temperature;	A n/a B n/a C n/a D 37%

aniline (62-53-3) → 1,2-diamino-benzene (95-54-5) + phenylhydrazine (100-63-0) + 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With chloroamine; cationic exchanger KU-23 In diethyl ether at 20℃; for 1.5h; Product distribution; var. time;	A 11% B 12% C 5%

methanol (67-56-1) + 5-oxo-1-phenyl-2,5-dihydro-1H-[1,2,3]triazole-4-carboxylic acid methyl ester; phenylhydrazine salt → diazomalonic acid methyl ester-anilide + phenylhydrazine (100-63-0)

benzenediazonium (2684-02-8) → phenylhydrazine (100-63-0)

Conditions	Yield
With alkali sulfite anschl. mit H2SO3;
With alkali sulfite anschl. mit Zink-Staub und Essigsaeure;
With hydrogenchloride; sodium sulfite
With sodium carbonate; sodium sulfite anschliessend Behandeln mit Schwefeldioxid und Erwaermen mit wss. Salzsaeure;
With alkali disulfite und anschl. Erhitzen mit HCl;

6-methyl-3-(1-phenylhydrazono-ethyl)-pyran-2,4-dione (29214-73-1) + furan-2,3,5(4H)-trione pyridine (1:1) → phenylhydrazine (100-63-0)

p-phenylene-bis-hydrazine-N,N'-dicarboxylic acid tetramethyl ester + furan-2,3,5(4H)-trione pyridine (1:1) → phenylhydrazine (100-63-0) + 1,4-phenylenediamine (106-50-3)

2,4-diphenyl-1-(2,4,5-trimethyl-phenyl)-2,5-dihydro-1H-[1,2,3]triazole + acetic acid (64-19-7) → phenylhydrazine (100-63-0)

benzenediazonium; hydroxide (54478-82-9) → phenylhydrazine (100-63-0)

Conditions	Yield
With zinc at 0℃;
With sulphurous acid

benzenediazonium sulphate → phenylhydrazine (100-63-0)

Conditions	Yield
With hydrogenchloride at 0℃; durch elektrolytische Reduktion an einer Quecksilber-Kathode;

N-benzyl-N-phenylhydrazine (614-31-3) → phenylhydrazine (100-63-0) + 1-benzyl-2-benzylidene-1-phenylhydrazine (2725-46-4)

benzene diazonium chloride (100-34-5) + triphenylphosphine (603-35-0) → phenylhydrazine (100-63-0)

Conditions	Yield
anschliessende Hydrolyse;

3-phenyl-carbazic acid ; phenylhydrazine salt (142877-70-1) → methylammonium carbonate (15719-64-9, 15719-76-3, 97762-63-5) + phenylhydrazine (100-63-0)

Conditions	Yield
im geschlossenen Rohr;

Menthone (10458-14-7) → phenylhydrazine (100-63-0)

Conditions	Yield
Kinetics; l-menthone;

1-anilinomalonyl-3-methyl-4-(4'-nitrobenzeneazo)-5-pyrazolone (75205-75-3) → 4-amino-N-hydroxybenzenamine (43019-69-8) + 1-anilinomalonyl-3-methyl-4-aminopyrazolone (125464-25-7) + 3-(4-Hydroxy-3-methyl-5-oxo-4,5-dihydro-pyrazol-1-yl)-3-oxo-N-phenyl-propionamide + phenylhydrazine (100-63-0)

Conditions	Yield
In water; N,N-dimethyl-formamide Mechanism; electrochemical reduction, buffer; pH range of 2-10;

3-(N-Nitro-N-phenylhydrazono)pentane-2,4-dione (129302-56-3) → 3-Aminopentan-2,4-dion (142414-84-4) + phenylhydrazine (100-63-0)

Conditions	Yield
In water; N,N-dimethyl-formamide at 25℃; Product distribution; Mechanism; coulometry: E = -1.8V, pH 2.5; variation of condition;

C6H5N2(1+)*O4S(1-) → bromobenzene (108-86-1) + biphenyl (92-52-4) + chlorobenzene (108-90-7) + phenylhydrazine (100-63-0) + benzene (71-43-2) + phenol (108-95-2)

Conditions	Yield
for 0.5h; Product distribution; Ambient temperature; in the absence and presence of reductant, stimulants ( SnCl2, Fe salts, ascorbic acid) and halide ions;

aniline (62-53-3) → 4-Aminobiphenyl (92-67-1) + 2-phenylaniline (90-41-5) + diphenylamine (122-39-4) + phenylhydrazine (100-63-0)

Conditions	Yield
With alkaline chloramine at 50℃; Product distribution; var. time;

benzaldehyde phenylhydrazone (588-64-7) → benzaldehyde (100-52-7) + phenylhydrazine (100-63-0)

Conditions	Yield
With hydrogenchloride; water In ethanol at 25℃; Rate constant; Thermodynamic data; Equilibrium constant; other cond.: further reagents; other obj. of st.: E(excit.), ΔH(excit.), -(DS(excit.));

hydrogenchloride (7647-01-0) + 3-(β-phenylhydrazono-phenethyl)-phthalide → phenylhydrazine (100-63-0)

hydrogenchloride (7647-01-0) + 3-(3-methyl-β-phenylhydrazono-phenethyl)-3H-benz[de]isochromen-1-one → phenylhydrazine (100-63-0)

5-methyl-3-phenyl-1,3,4-oxadiazol-2(3H)-one (28740-63-8) + alcoholic ammonium sulfide solution → phenylhydrazine (100-63-0)

Conditions	Yield
at 100℃;

(5-methyl-3-phenyl-3H-[1,3,4]oxadiazol-2-ylidene)-phenyl-amine + alcoholic KOH-solution → phenylhydrazine (100-63-0)

pyridine-2-carbaldehyde (1121-60-4) + phenylhydrazine (100-63-0) → (E)-1-(2-pyridinyl)methylene-2-phenylhydrazine (30915-38-9)

Conditions	Yield
In ethanol for 6h; Reflux;	100%
With acetic acid In ethanol for 3h; Reflux;	91%
With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; water at 20℃; for 0.666667h; Green chemistry;	85%

succinic acid anhydride (108-30-5) + phenylhydrazine (100-63-0) → 4-oxo-4-(2-phenylhydrazinyl)butanoic acid (14580-01-9)

Conditions	Yield
In acetonitrile at 20℃; for 24h;	100%
With ethanol

acetic anhydride (108-24-7) + phenylhydrazine (100-63-0) → 1-acetyl-2-phenylhydrazine (114-83-0)

Conditions	Yield
In diethyl ether at 0℃; for 10h;	100%
Stage #1: phenylhydrazine With triethylamine In dichloromethane at 0℃; Inert atmosphere; Stage #2: acetic anhydride In dichloromethane at 0 - 20℃; Inert atmosphere;	97%
With pyridine; aluminum oxide at 90 - 92℃; for 1h; microwave irradiation;	65%

4-methyl-benzaldehyde (104-87-0) + phenylhydrazine (100-63-0) → 4-methylbenzaldehyde phenylhydrazone (2829-25-6)

Conditions	Yield
With pyridinium p-toluenesulfonate In dichloromethane	100%
In neat (no solvent) at 20℃; for 0.00277778h;	97%
With oxidized single-walled carbon nanotubes(SWCNs-COOH) In ethanol at 80℃; for 1.25h;	96%

ethyl acetoacetate (141-97-9) + phenylhydrazine (100-63-0) → edaravone (89-25-8)

Conditions	Yield
In acetic acid Heating;	100%
for 0.166667h; Irradiation;	100%
at 0 - 90℃; for 1.5h;	100%

2-chloro-benzaldehyde (89-98-5) + phenylhydrazine (100-63-0) → 2-chlorobenzaldehyde phenylhydrazone (34158-76-4)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 160℃; for 0.166667h; microwave irradiation;	100%
With pyridinium p-toluenesulfonate In dichloromethane	100%

4-chloro-benzoyl chloride (122-01-0) + phenylhydrazine (100-63-0) → 2-(4-Chlorbenzoyl)-1-phenylhydrazid (15089-07-3)

Conditions	Yield
With pyridine In tetrahydrofuran at 5 - 20℃; for 2h;	100%
With pyridine for 20h;	70%
With pyridine

cyclotridecanone (832-10-0) + phenylhydrazine (100-63-0) → 5,6,7,8,9,10,11,12,13,14,15,16-dodecahydrocyclotridecan[b]indole (7140-32-1)

Conditions	Yield
With trichloroacetic acid at 100℃; for 0.0833333h; Fischer indole synthesis;	100%
With hydrogenchloride; acetic acid

benzaldehyde (100-52-7) + phenylhydrazine (100-63-0) → (E)-1-benzylidene-2-phenylhydrazine (588-64-7)

Conditions	Yield
In ethanol for 6h; Reflux;	100%
In water for 0.0833333h; Sonication;	95%
With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; water at 20℃; for 0.666667h; Reagent/catalyst; Solvent; Concentration; Green chemistry;	91%

3-phenyl-propenal (104-55-2) + phenylhydrazine (100-63-0) → cinnamaldehyde phenylhydrazone (1216-15-5)

Conditions	Yield
piperidine In ethanol for 5h; Heating;	100%
With oxidized single-walled carbon nanotubes(SWCNs-COOH) In ethanol at 80℃; for 0.75h;	98%
With Dowex resin acid form In ethanol for 0.75h;	88%

2-Adamantanone (700-58-3) + phenylhydrazine (100-63-0) → 1-(adamantan-2-ylidene)-2-phenylhydrazine (94658-14-7)

Conditions	Yield
In dichloromethane at 20℃; for 2h; Inert atmosphere;	100%
In ethanol; acetic acid	98%
With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; water at 20℃; for 0.583333h; Green chemistry;	82%
With acetic acid for 0.25h; Ambient temperature;

2-carbethoxy-<11>-α-cyclothien-1-one (20894-58-0) + phenylhydrazine (100-63-0) → 2-(Phenyl-hydrazono)-16-thia-bicyclo[11.2.1]hexadeca-1(15),13-diene-3-carboxylic acid ethyl ester

Conditions	Yield
In toluene at 110℃; for 1h;	100%

2-bromophenyl methyl ketone (2142-69-0) + phenylhydrazine (100-63-0) → N-[1-(2-Bromo-phenyl)-eth-(Z)-ylidene]-N'-phenyl-hydrazine (1011736-72-3)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 160℃; for 0.166667h; microwave irradiation;	100%
In diethyl ether Heating;
With acetic acid In ethanol for 0.166667h; Heating; Yield given;

2,2,2-trichloro-1-(4-chlorophenyl)ethanone (27704-37-6) + phenylhydrazine (100-63-0) → 2-(4-Chlorbenzoyl)-1-phenylhydrazid (15089-07-3)

Conditions	Yield
With triethylamine In hexane at 25℃; for 3h;	100%

N,N-Dimethyl-2,4-bis(trifluoroacetyl)-1-naphthylamine (115975-33-2) + phenylhydrazine (100-63-0) → 2,2,2-trifluoro-1-(2-phenyl-3-(trifluoromethyl)-2H-benzo[g]indazol-5-yl)ethanone (129602-66-0)

Conditions	Yield
In acetonitrile for 24h; Heating;	100%

2-ethyl-4-oxo-1,3-benzoxazinium perchlorate (56429-60-8) + phenylhydrazine (100-63-0) → 2-(5-Ethyl-2-phenyl-2H-[1,2,4]triazol-3-yl)-phenol (120029-39-2)

Conditions	Yield
In acetic acid Heating;	100%

4-Dimethylaminomethylene-2,6-dimethyl-heptane-3,5-dione (85302-03-0) + phenylhydrazine (100-63-0) → 1-(5-Isopropyl-1-phenyl-1H-pyrazol-4-yl)-2-methyl-propan-1-one (85302-09-6)

Conditions	Yield
In acetic acid; butan-1-ol for 1h; Heating;	100%

2-((dimethylamino)methylene)-1,3-diphenylpropane-1,3-dione (85302-05-2) + phenylhydrazine (100-63-0) → 4-Benzoyl-1,5-diphenyl-pyrazol (85302-11-0)

Conditions	Yield
In acetic acid; butan-1-ol for 3h; Heating;	100%
In ethanol at 20℃; for 12h; Solvent; Inert atmosphere; regioselective reaction;	89%

2-(4-chloro-phenyl)-benzo[e][1,3]oxazin-4-one; perchlorate (73389-18-1) + phenylhydrazine (100-63-0) → 2-[5-(4-Chloro-phenyl)-2-phenyl-2H-[1,2,4]triazol-3-yl]-phenol (120029-44-9)

Conditions	Yield
In acetic acid Heating;	100%

phenylhydrazine (100-63-0) + Glyoxilic acid (298-12-4) → phenylhydrazonoacetic acid (6000-60-8)

Conditions	Yield
With hydrogenchloride In water	100%
In water at 20℃; for 1h;	95%
With hydrogenchloride In water at 0 - 20℃; for 1h;	94%

phenylhydrazine (100-63-0) + cycloheptanone (502-42-1) → 5,6,7,8,9,10-hexahydrocyclohept[b]indole (2047-89-4)

Conditions	Yield
With trichloroacetic acid at 100℃; for 0.0833333h; Fischer indole synthesis;	100%
With 1,3-bis(3-sulfopropyl)-1H-imidazol-3-ium hydrogensulfate In water at 80℃; for 1h; Fischer indole synthesis;	88%
With acetic acid for 0.5h; Heating;	74%

phenylhydrazine (100-63-0) + 1,3-Diphenylpropanone (102-04-5) → 2-benzyl-3-phenyl-1H-indole (4679-91-8)

Conditions	Yield
With trichloroacetic acid at 100℃; for 0.0833333h; Fischer indole synthesis;	100%
With phosphorus trichloride In benzene	80%
With Amberlite IR 120 In ethanol at 80℃; for 12h; Fischer Indole Synthesis;	80%
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at 110℃; for 0.25h; Fischer indole synthesis; Microwave irradiation; Sealed vessel;	77%

1-(2-chloro-phenyl)-3-phenyl-2-propen-1-one (144017-77-6, 20426-47-5) + phenylhydrazine (100-63-0) → 1,5-diphenyl-3-(o-chlorohenyl)pyrazoline

Conditions	Yield
With acetic acid In ethanol for 0.5h; Heating;	100%

phenylhydrazine (100-63-0) + ortho-bromobenzaldehyde (6630-33-7) → 2-Brombenzaldehyd-Phenylhydrazon (10407-11-1)

Conditions	Yield
	100%

phenylhydrazine (100-63-0) + 5-methylthio-2-selenophenethiol → N-[5-Methylsulfanyl-4-(5-methylsulfanyl-selenophen-2-ylsulfanyl)-dihydro-selenophen-(2E)-ylidene]-N'-phenyl-hydrazine

Conditions	Yield
With water	100%

(Z)-methyl 2-hydroxy-4-oxo-4-(o-tolyl)but-2-enoate + phenylhydrazine (100-63-0) → methyl 5-(2-methylphenyl)-1-phenylpyrazole-3-carboxylate (235789-32-9)

Conditions	Yield
With acetic acid for 2h; Heating;	100%

phenylhydrazine (100-63-0) + ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate (113161-58-3) → ethyl 3-diethoxyphosphoryl-3,3-difluoro-2-(phenylhydrazono)propionate

Conditions	Yield
In benzene for 2h; Substitution;	100%

phenylhydrazine (100-63-0) + (E)-benzalacetone (1896-62-4) → (E)-1-phenyl-2-((E)-4-phenylbut-3-en-2-ylidene)hydrazine (358723-67-8)

Conditions	Yield
at 20℃; for 0.0833333h;	100%
With acetic acid In methanol at 20℃; Inert atmosphere;	85%
With acetic acid In methanol for 0.75h; Heating;
With acetic acid In methanol at 20℃;

phenylhydrazine (100-63-0) + S-tert-butyl cyclohexylcarbamoylthioacetate (339274-36-1) → N-Cyclohexyl-2-(N'-phenyl-hydrazinocarbonyl)-acetamide (62970-56-3)

Conditions	Yield
With silver trifluoroacetate In 1,2-dimethoxyethane at 20℃;	100%

phenylhydrazine (100-63-0) + 4,4,4-trifluoro-1-(2-fluorophenyl)butane-1,3-dione (111102-82-0) → 5-(2-fluorophenyl)-1-phenyl-3-trifluoromethylpyrazole

Conditions	Yield
With sulfuric acid In ethanol	100%

Upstream product

• 532-11-6 anethole trithione 
• 100-46-9 benzylamine 
• 114698-73-6 3-phenyl-1-(1H-tetrazol-5-yl)-tetraz-1-ene 
• 64-17-5 ethanol 
• 10035-10-6 hydrogen bromide 
• 148-97-0 N-hydroxy-N-nitroso-benzenamine 
• 7647-01-0 hydrogenchloride 
• 343361-09-1 (E)-1-phenyl-2-((E)-3-phenylallylidene)hydrazone 
• 618-40-6 1-Methyl-1-phenylhydrazine 
• 5810-79-7 2-(phenylamino)-1H-benzo[de]isoquinoline-1,3(2H)-dione 
• 114-83-0 1-acetyl-2-phenylhydrazine 
• 108-86-1 bromobenzene 
• 1420711-86-9 [RuCl(η²-phenylhydrazine)(η³-tris[2-(diisopropylphosphino)ethyl]phosphine)]Cl 
• 591-50-4 iodobenzene 

Downstream Products

• 109729-14-8 3-methyl-4,6-diphenyl-6H-pyrazolo[4,3-d]isoxazole 
• 59677-66-6 2-phenylhydrazonothiazolidin-4-one 
• 4413-30-3 N,N'-diphenyl-C-methylformazan 
• 955-84-0 1-[2]pyridyl-propan-1-one-phenylhydrazone 
• 100142-57-2 5-hydroxymethyl-furan-2-carbaldehyde-phenylhydrazone 
• 949-87-1 4-Methylazobenzol 
• 87613-35-2 1-(5-methyl-isoxazol-3-yl)-ethanone phenylhydrazone 
• 58589-69-8 3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-amine 
• 123102-61-4 3-methyl-4-(3-phenyl-hydrazinocarbonyl)-crotonic acid 
• 36141-18-1 2-(1-phenyl-1H-pyrazol-3-yl)-aniline 
• 100705-54-2 1-isopropyl-pyrrolidine-2,3-dione-3-phenylhydrazone 
• 62221-94-7 2-phenyl-1,2,4,5,6,7-hexahydro-indazol-3-one 
• 5439-98-5 2-phenyl-2,3-dihydro-phthalazine-1,4-dione 
• 108717-95-9 3-(5-methyl-2-phenyl-2H-pyrazol-3-yl)-pyridine 

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Comparison between 1-methylPhenylhydrazine (cas 100-63-0) and Phenylhydrazine (cas 100-63-0) in the S1 state: Structure, energies and lifetime07/26/2019

Based on the theoretical and REMPI spectroscopic study, a comparison between 1-methylphenylhydrazine and phenylhydrazine in the excited S1 state is conducted to reveal the formation and influence of p–p–π conjugation. The ab initio and DFT calculations predict that phenylhydrazine and 1-methy...detailed

In situ observation of ninhydrin and Phenylhydrazine (cas 100-63-0) reaction in solution by FTIR07/24/2019

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Phenylhydrazine (cas 100-63-0) administration accelerates the development of experimental cerebral malaria07/22/2019

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A novel potent metal-binding NDM-1 inhibitor was identified by fragment virtual, SPR and NMR screening

NDM-1 can hydrolyze nearly all available β-lactam antibiotics, including carbapenems. NDM-1 producing bacterial strains are worldwide threats. It is still very challenging to find a potent NDM-1 inhibitor for clinical use. In our study, we used a metal-binding pharmacophore (MBP) enriched virtual fragment library to screen NDM-1 hits. SPR screening helped to verify the MBP virtual hits and identified a new NDM-1 binder and weak inhibitor A1. A solution NMR study of 15N-labeled NDM-1 showed that A1 disturbed all three residues coordinating the second zinc ion (Zn2) in the active pocket of NDM-1. The perturbation only happened in the presence of zinc ion, indicating that A1 bound to Zn2. Based on the scaffold of A1, we designed and synthesized a series of NDM-1 inhibitors. Several compounds showed synergistic antibacterial activity with meropenem against NDM-1 producing K. pneumoniae.

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Synthesis and Characterization of Telmisartan-Derived Cell Death Modulators to Circumvent Imatinib Resistance in Chronic Myeloid Leukemia

New strategies to eradicate cancer stem cells in chronic myeloid leukemia (CML) include a combination of imatinib with peroxisome proliferator-activated receptor gamma (PPARγ) ligands. Recently, we identified the partial PPARγ agonist telmisartan as effective sensitizer of resistant K562 CML cells to imatinib treatment. Here, the importance of the heterocyclic core on the cell death-modulating effects of the telmisartan-derived lead 4′-((2-propyl-1H-benzo[d]imidazol-1-yl)methyl)-[1,1′-biphenyl]-2-carboxylic acid (3 b) was investigated. Inspired by the pharmacodynamics of HYL-6d and the selective PPARγ ligand VSP-51, the benzimidazole was replaced by a carbazole or an indole core. The results indicate no correlation between PPARγ activation and sensitization of resistant CML cells to imatinib. The 2-COOH derivatives of the carbazoles or indoles achieved low activity at PPARγ, while the benzimidazoles showed 60-100 % activation. Among the 2-CO2CH3 derivatives, only the ester of the lead (2 b) slightly activated PPARγ. Sensitizing effects were further observed for this non-cytotoxic 2 b (80 % cell death), and to a lesser extent for the lead 3 b or the 5-Br-substituted ester of the benzimidazoles (5 b).

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Discovery of novel inhibitors of human phosphoglycerate dehydrogenase by activity-directed combinatorial chemical synthesis strategy

Serine, the source of the one-carbon units essential for de novo purine and deoxythymidine synthesis plays a crucial role in the growth of cancer cells. Phosphoglycerate dehydrogenase (PHGDH) which catalyzes the first, rate-limiting step in de novo serine biosynthesis has become a promising target for the cancer treatment. Here we identified H-G6 as a potential PHGDH inhibitor from the screening of an in-house small molecule library based on the enzymatic assay. We adopted activity-directed combinatorial chemical synthesis strategy to optimize this hit compound. Compound b36 was found to be the noncompetitive and the most promising one with IC50 values of 5.96 ± 0.61 μM against PHGDH. Compound b36 inhibited the proliferation of human breast cancer and ovarian cancer cells, reduced intracellular serine synthesis, damaged DNA synthesis, and induced cell cycle arrest. Collectively, our results suggest that b36 is a novel PHGDH inhibitor, which could be a promising modulator to reprogram the serine synthesis pathway and might be a potential anticancer lead worth further exploration.

Cross-Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate-Determining Deprotonation of Bound Hydrazine

Reported here is the Pd-catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate-limiting deprotonation of a hydrazine-bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.