80-11-5

Basic information

• Product Name: N-Methyl-N-nitrosotoluene-4-sulphonamide
• Synonyms: Benzenesulfonamide, N,4-dimethyl-N-nitroso-;Benzenesulfonamide,N,4-dimethyl-N-nitroso-;Diazale;diazalo;Methylnitroso-p-toluenesulfonamide;n,4-dimethyl-n-nitroso-benzenesulfonamid;N,4-dimethyl-N-nitroso-Benzenesulfonamide;N,4-Dimethyl-N'-oxobenzenesulfonohydrazide
• CAS NO: 80-11-5
• Molecular Formula: C₈H₁₀N₂O₃S
• Molecular Weight: 214.24
• EINECS: 201-252-6
• Product Categories: Pharmaceutical Intermediates;Amines;Aromatics;Sulfur & Selenium Compounds
• Mol File: 80-11-5.mol
• Article Data: 10

Chemical Properties

• Melting Point: ~58 °C
• Boiling Point: 320.5 °C at 760 mmHg
• Flash Point: 147.6 °C
• Appearance: pale yellow crystalline powder
• Density: 1.3844 (rough estimate)
• Refractive Index: 1.5690 (estimate)
• Storage Temp.: 2-8°C
• PKA: -19.25±0.70(Predicted)
• Stability: Stable, but heat sensitive; may also be light sensitive. Incompatible with strong oxidizing agents, alkalies.
• Merck: 13,9621
• CAS DataBase Reference: N-Methyl-N-nitrosotoluene-4-sulphonamide(CAS DataBase Reference)
• NIST Chemistry Reference: N-Methyl-N-nitrosotoluene-4-sulphonamide(80-11-5)
• EPA Substance Registry System: N-Methyl-N-nitrosotoluene-4-sulphonamide(80-11-5)

Safety Data

• Hazard Codes: E,Xi,Xn
• Statements: 2-36/37/38-43-20/21/22
• Safety Statements: 15-26-35-36/37-36
• RIDADR: UN 3234 4.1/PG 2
• WGK Germany: 2
• RTECS: XT5950000
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 80-11-5(Hazardous Substances Data)

Usage

Chemical Properties

pale yellow crystalline powder

Uses

Different sources of media describe the Uses of 80-11-5 differently. You can refer to the following data:
1. N-Methyl-N-nitroso-p-toluenesulfonamide is Diazomethane precursor.
2. In the laboratory preparation of diazomethane. Directions for use: de Boer, Backer, Rec. Trav. Chim. 73, 232 (1954).

Purification Methods

Crystallise diazald from *benzene by addition of pet ether and store it in a refrigerator. It is soluble in most organic solvents and liberates diazomethane on treatment with alkali. Store it in the cold. [deBoer & Backer Org Synth 34 96 1954, Beilstein 11 I 29.]

InChI:InChI=1/C8H10N2O3S/c1-5-3-4-7(10-11)6(2)8(5)14(9,12)13/h3-4H,1-2H3,(H2,9,12,13)

Synthetic route

N-methyl-p-toluenesulfonylamide (640-61-9) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
With hydrogenchloride; water; sodium nitrite In diethyl ether	81%
With perchloric acid; sodium nitrite In dichloromethane; water Rate constant; Equilibrium constant; nitrosation of substituted N-methylbenzenesulfonamides; reversibility; kinetics of nitrosation and denitrosation; substituent effect; acid catalysis; effect of nucleophiles; mechanism;
With dinitrogen tetraoxide

p-toluenesulfonyl chloride (98-59-9) + methylamine (74-89-5) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
With sodium hydroxide Behandeln des Reaktionsgemisches mit Essigsaeure und NaNO2;

cyclopentyl nitrite (67764-33-4) + N-methyl-p-toluenesulfonylamide (640-61-9) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
With diluted acid

1-methyl-1-(4-tolylsulfonyl)hydrazine (22547-51-9) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
With trifluoroacetic acid; sodium nitrite

p-toluenesulfonyl chloride (98-59-9) + (Z)-potassium methanediazotate (3058-37-5) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
In diethyl ether

C8H10NO2S(1-) (103999-21-9) → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
With nitrosonium perchlorate In acetonitrile at 25℃; Thermodynamic data;

N-methyl-N-(t-butoxycarbonyl)-p-toluenesulfonamide → N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: trifluoroacetic acid / neat (no solvent) / 1 h / 0 - 23 °C 2: sodium chloride; sodium acetate; sodium nitrite; acetic acid / water / 0.25 h / 0 °C View Scheme

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → N-methyl-p-toluenesulfonylamide (640-61-9)

Conditions	Yield
With sulfite(2-) In 1,4-dioxane; water at 25℃; Rate constant;	100%
With Thiocyanate In 1,4-dioxane; water at 25℃; Rate constant;	100%
With thiourea In 1,4-dioxane; water at 25℃; Rate constant;	100%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + N-Boc-D-serine(Bzl)-OH (47173-80-8) → (R)-3-benzyloxy-2-tert-butoxycarbonyl-amino-propionic acid methyl ester (67389-47-3)

Conditions	Yield
	99%

2-Amino-5-methylbenzoic acid (2941-78-8) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → 2-amino-5-methylbenzoic acid methyl ester (18595-16-9)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In diethyl ether; water Stage #2: 2-Amino-5-methylbenzoic acid In diethyl ether for 1h;	99%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 2-amino-5-fluorobenzoic acid (446-08-2) → 2-amino-5-fluoro-benzoic acid methyl ester (319-24-4)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In diethyl ether; water Stage #2: 2-amino-5-fluorobenzoic acid In diethyl ether for 1h;	99%

p-(chloromethyl)benzoyl chloride (876-08-4) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → p-(diazoacetyl)benzyl chloride (1137172-09-8)

Conditions	Yield
With triethylamine; sodium hydroxide In water; Petroleum ether for 2h;	99%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 4-methoxybenzoic acid (100-09-4) → methyl 4-methoxybenzoate (121-98-2)

Conditions	Yield
With potassium hydroxide In tetrahydrofuran; methanol; water at 20℃;	99%
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: 4-methoxybenzoic acid In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 25℃; Sonication;	89%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + (E)-methyl 3-(4-ethoxyphenyl)prop-2-enoate (87711-71-5) → methyl trans-2-(4-ethoxyphenyl)cyclopropanecarboxylate

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In 2-ethoxy-ethanol; diethyl ether; water at 60 - 70℃; Stage #2: (E)-methyl-3-(4-ethoxyphenyl)prop-2-enoate With palladium diacetate In diethyl ether at -25 - 20℃;	99%

tungsten hexacarbonyl (14040-11-0) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + C12H19Na → [(η5-C5Me4nPr)W(NO)(CO)2]

Conditions	Yield
Stage #1: tungsten hexacarbonyl; C12H19Na In tetrahydrofuran at 78℃; for 96h; Stage #2: N-methyl-N-nitrosotoluene-p-sulfonamide In tetrahydrofuran for 2h;	99%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 3-Carboxyphenol (99-06-9) → methyl 3-hydroxybenzoate (19438-10-9)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: 3-Carboxyphenol In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 25℃; Sonication;	99%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 4-methoxy-benzoyl chloride (100-07-2) → 2-chloro-1-(4-methoxyphenyl)ethanone (2196-99-8)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: 4-methoxy-benzoyl chloride In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 30℃; for 1.5h; Sonication; Stage #3: With hydrogenchloride In methanol; diethyl ether; water; N,N-dimethyl-formamide for 1h;	99%

1-nitro-3-vinyl-benzene (586-39-0) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → 1-cyclopropyl-3-nitrobenzene (22396-07-2)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: 1-nitro-3-vinyl-benzene With palladium diacetate In tetrahydrofuran; methanol; diethyl ether; water; N,N-dimethyl-formamide at 0℃;	99%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 2-amino-6-methylbenzoic acid (4389-50-8) → 2-amino-6-methylbenzoic acid methyl ester (18595-13-6)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In diethyl ether; water Stage #2: 2-amino-6-methylbenzoic acid In diethyl ether for 1h;	98%

2-methyl-1,3-dithian (6007-26-7) + (benzene)tricarbonylchromium (697302-50-4, 697302-51-5, 12082-08-5, 697302-53-7) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → [(η(5)-C6H6C(Me)S(CH2)3S)Cr(CO)2(NO)]

Conditions	Yield
With n-BuLi In tetrahydrofuran; hexane N2-atmosphere; stirring (0°C, 1.5 h), Cr-complex addn., stirring (0°C, 0.5 h), Diazald addn. (-78°C), to room temp. (2 h); filtering, evapn. (vac.), chromy. (alumina, n-hexane), evapn. (vac.); elem. anal.;	98%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 4-nitro-benzoic acid (62-23-7) → 4-nitrobenzoic acid methyl ester (619-50-1)

Conditions	Yield
With potassium hydroxide In tetrahydrofuran; methanol; water at 20℃;	98%
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: 4-nitro-benzoic acid In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 25℃; Sonication;	90%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + benzoic acid (65-85-0) → benzoic acid methyl ester (93-58-3)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: benzoic acid In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 25℃; Sonication;	97%
With potassium hydroxide In tetrahydrofuran; methanol; water at 20℃;	80%
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In ethoxyethoxyethanol; water; isopropyl alcohol at 60℃; Stage #2: benzoic acid In n-heptane; tert-butyl methyl ether at 20℃; Product distribution / selectivity;	62%
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With water; sodium hydrogencarbonate In tetrahydrofuran Stage #2: benzoic acid With ethoxyethoxyethanol In tetrahydrofuran	60 %Chromat.

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 3β-hydroxycopalic acid (872979-45-8) → C22H36O3

Conditions	Yield
With potassium hydroxide In diethyl ether at 0 - 100℃;	97%

2-amino-3-methoxybenzoic acid (3177-80-8) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → methyl 2-amino-3-methoxybenzoate (5121-34-6)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In diethyl ether; water Stage #2: 2-amino-3-methoxybenzoic acid In diethyl ether for 1h;	96%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + glutaric acid monobenzyl ester (54322-10-0) → 6-bromo-5-oxo-hexanoic acid benzyl ester (1029126-16-6)

Conditions	Yield
Stage #1: glutaric acid monobenzyl ester With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 1.45h; Inert atmosphere; Stage #2: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In diethyl ether; dichloromethane at 0℃; for 1.5h; Stage #3: With hydrogen bromide In diethyl ether; dichloromethane; water at 0℃; for 0.5h;	96%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + (±)-5,4'-diacetoxy-7-hydroxyflavan-4-one → (±)-5,4'-diacetoxy-7-methoxyflavan-4-one (749256-67-5)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In ethanol; water Stage #2: (±)-5,4'-diacetoxy-7-hydroxyflavan-4-one In diethyl ether; dichloromethane at 20℃; for 20h;	95%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + Cinnamic acid (621-82-9) → methyl cinnamate (103-26-4)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: Cinnamic acid In methanol; diethyl ether; water; N,N-dimethyl-formamide at 0 - 25℃; Sonication;	95%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + methyl cinnamate (103-26-4) → methyl trans-2-phenylcyclopropanecarboxylate (5861-31-4, 16205-72-4)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: methyl cinnamate With palladium diacetate In tetrahydrofuran; methanol; diethyl ether; water; N,N-dimethyl-formamide at 0℃;	95%

stilbene (588-59-0) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → trans-1,2-diphenylcyclopropane (1138-47-2)

Conditions	Yield
Stage #1: N-methyl-N-nitrosotoluene-p-sulfonamide With potassium hydroxide In methanol; water; N,N-dimethyl-formamide Flow reactor; Stage #2: stilbene With palladium diacetate In tetrahydrofuran; methanol; diethyl ether; water; N,N-dimethyl-formamide at 0℃;	94%

xanthone-2-carboxylic acid (40274-67-7) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → xanthone-2-carboxylic acid methyl ester (42946-50-9)

Conditions	Yield
With potassium hydroxide In ethanol; dichloromethane at 0℃;	93%

isopropenylcyclopentadienyllithium (77060-52-7) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + molybdenum hexacarbonyl (13939-06-5, 199620-15-0) → (η5-isopropenylcyclopentadienyl)dicarbonylnitrosylmolybdenum (80340-00-7)

Conditions	Yield
	93%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + lithium (1-methylethenyl)cyclopentadiene (77060-52-7) + molybdenum hexacarbonyl (13939-06-5, 199620-15-0) → (η5-isopropenylcyclopentadienyl)dicarbonylnitrosylmolybdenum (80340-00-7)

Conditions	Yield
In tetrahydrofuran to lithium isopropenylcyclopentadienide and Mo(CO)6 THF was added, a mixture was refluxed for 46 h, MeN(NO)SO2C6H4Me was added at 25°C and stirred for 1 h, N2 atm.; evapn. in vac., extn. (pentane), evapn. on silica gel in vac., column chromy. (silica gel, pentane), recrystn. (pentane, -78°C, under N2); elem. anal.;	93%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 4-chloro-benzoyl chloride (122-01-0) → p-chlorophenacyl chloride (937-20-2)

Conditions	Yield
With potassium hydroxide In tetrahydrofuran; methanol; water at 20℃; Arndt-Eistert Homologation;	93%

4-Bromobenzoic acid (586-76-5) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → 4-methoxycarbonylphenyl bromide (619-42-1)

Conditions	Yield
With potassium hydroxide In tetrahydrofuran; methanol; water at 20℃;	93%

gymnastatin N + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) → methyl 2-[(2E,4E)-4,6-dimethyldodeca-2,4-dienamido]-3-(4-hydroxyphenyl)-propanoate

Conditions	Yield
With potassium hydroxide; ethoxyethoxyethanol In diethyl ether at 0℃; for 3h;	92%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + 10,10-dichlorobicyclo<6.2.0>dec-4-ene-9-one (13866-30-3, 92590-04-0) → (Z)-1,1-Dichloro-1,3,3a,4,5,8,9,9a-octahydro-cyclopentacycloocten-2-one (92007-24-4, 92590-05-1)

Conditions	Yield
With potassium hydroxide In methanol; diethyl ether; water at 20℃; Inert atmosphere;	92%

N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + (4-(1,4-epoxynaphthalen-1(4H)-yl)butoxy)(tert-butyl)dimethylsilane → tert-butyldimethyl(4-(1,1a,7,7a-tetrahydro-2H-2,7-epoxycyclopropa[b]naphthalen-2-yl)butoxy)silane

Conditions	Yield
With palladium diacetate; sodium hydroxide In tetrahydrofuran; ethanol; water Inert atmosphere;	92%

Upstream product

• 640-61-9 N-methyl-p-toluenesulfonylamide 
• 103999-21-9 C₈H₁₀NO₂S^(1-) 
• 56805-36-8 N-methyl-N-(t-butoxycarbonyl)-p-toluenesulfonamide 
• 98-59-9 p-toluenesulfonyl chloride 
• 3058-37-5 (Z)-potassium methanediazotate 
• 22547-51-9 1-methyl-1-(4-tolylsulfonyl)hydrazine 
• 67764-33-4 cyclopentyl nitrite 
• 74-89-5 methylamine 

Downstream Products

• 80-48-8 methyl p-toluene sulfonate 
• 26541-51-5 N-nitroso thiomorpholine 
• 640-61-9 N-methyl-p-toluenesulfonylamide 
• 5632-47-3 N-nitrosopiperazine 
• 88381-44-6 N-nitrosothiazolidine-4-carboxylic acid 
• 621-64-7 N-nitroso-N,N-dipropylamine 
• 36475-59-9 C₂H₇N₃O 
• 55-18-5 N-Nitrosodiethylamine 
• 937-40-6 Benzylmethylnitrosamin 
• 29104-67-4 2-Nitroso-2,5-diazahexan 
• 67389-47-3 (R)-3-benzyloxy-2-tert-butoxycarbonyl-amino-propionic acid methyl ester 
• 85636-86-8 methyl 9-oxo-9H-xanthene-1-carboxylate 
• 104-15-4 toluene-4-sulfonic acid 

Relevant articles and documents

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