103-34-4

Basic information

• Product Name: Morpholine, 4,4'-dithiobis-
• Synonyms: SULFASAN(R) R;Morpholine N,N'-disulfide;N,N'-DIMORPHOLINE DISULFIDE;N,N'-DITHIOBIS(MORPHOLINE);VANAX A;VANAX A FINE GRIND;VANAX A RODFORM;4,4'-DITHIODIMORPHOLINE
• CAS NO: 103-34-4
• Molecular Formula: C₈H₁₆N₂O₂S₂
• Molecular Weight: 236.35
• EINECS: 203-103-0
• Product Categories: Rubber Chemicals;Industrial/Fine Chemicals;SULFUR DONOR;rubber vulcanizing accelerator
• Mol File: 103-34-4.mol
• Article Data: 11

Chemical Properties

• Melting Point: 124-125°C
• Boiling Point: 371.7 °C at 760 mmHg
• Flash Point: 154 °C
• Appearance: white to off-white crystalline powder
• Density: 1.32~1.38g/cm3
• Vapor Pressure: 0.004Pa at 25℃
• Refractive Index: 1.6300 (estimate)
• Storage Temp.: Refrigerator
• PKA: 0.78±0.20(Predicted)
• Water Solubility: 215mg/L at 20.2℃
• Merck: 14,3372
• CAS DataBase Reference: Morpholine, 4,4'-dithiobis-(CAS DataBase Reference)
• NIST Chemistry Reference: Morpholine, 4,4'-dithiobis-(103-34-4)
• EPA Substance Registry System: Morpholine, 4,4'-dithiobis-(103-34-4)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• RTECS: QE3325000
• Hazardous Substances Data: 103-34-4(Hazardous Substances Data)

Usage

General Description

Morpholine, 4,4'-dithiobis-, also known as DTDM, is a dithiocarbamate compound containing two morpholine rings connected by a central sulfur-sulfur (S-S) bond. Morpholine, 4,4'-dithiobis- is widely used in the rubber industry as a vulcanization accelerator.

Flammability and Explosibility

Nonflammable

Purification Methods

Crystallise it from hot aqueous dimethylformamide or EtOH. It is a fungicide. [Blake J Am Chem Soc 65 1267 1943.]

InChI:InChI=1/2C4H9NO.2S/c2*1-3-6-4-2-5-1;;/h2*5H,1-4H2;;/q;;2*-2

Synthetic route

morpholine (110-91-8) → 4,4'-dithiodimorpholine (103-34-4)

Conditions	Yield
With disulfur dichloride; sodium phosphate at 20℃; for 2h; Reagent/catalyst; Temperature;	95.85%
With disulfur dichloride; sodium hydroxide In dichloromethane; water Cooling with ice;	84.7%
With disulfur dichloride; sodium hydroxide In hexane; water 1.) 0 deg C 2.) r.t.;	80%

morpholino dithionitrite (139558-39-7) → 4,4'-dithiodimorpholine (103-34-4)

Conditions	Yield
In hexane; benzene for 0.5h; Heating;	74%

morpholine (110-91-8) + thiocamphor (53402-10-1) → N,N'-thiodimorpholine (5038-11-9) + 4,4'-dithiodimorpholine (103-34-4) + 1,11,11-trimethyl-3,4,5,6-tetrathia-tricyclo[6.2.1.0(2,7)]undeca-2(7)-ene + 1,12,12-trimethyl-3,4,5,6,7-pentathiatricyclo[7.2.1.0(2,8)]dodeca-2(8)-ene

Conditions	Yield
Stage #1: thiocamphor With disulfur dichloride In dichloromethane at 20℃; for 0.166667h; Stage #2: morpholine In dichloromethane at 20℃; for 1h;	A 10% B 60% C n/a D n/a

N,N'-thiodimorpholine (5038-11-9) → dimorpholinotrisulfide (16131-52-5) + 4,4'-dithiodimorpholine (103-34-4) + N,N'-tetrathiobismorpholine (16131-53-6)

Conditions	Yield
With boron trifluoride diethyl etherate Ambient temperature;	A 18% B 6% C 24%

morpholine (110-91-8) → N,N'-thiodimorpholine (5038-11-9) + 4,4'-dithiodimorpholine (103-34-4)

Conditions	Yield
With sulfur; iodine In pyridine Product distribution; Heating; effect of amount of S8; other solvent;

4,4'-dithiodimorpholine (103-34-4) + thiourea (17356-08-0) → C5H11N3OS3

Conditions	Yield
In methanol Mechanism; Ambient temperature; also with N,N'-thio- and N,N'-dithiobisamides, other temperature;	90%
In methanol Ambient temperature;	90%

4,4'-dithiodimorpholine (103-34-4) + copper(II) perchlorate hexahydrate + acetonitrile (75-05-8) → tetrakis(acetonitrile)copper(I) perchlorate (14057-91-1)

Conditions	Yield
In acetonitrile byproducts: SO2, O(CH2CH2)2NH2ClO4, HClO4; (N2); stirring at ambient temp.; disolution in hot CH3CN; filtration; evapn.; elem. anal.; NMR;	88%

4,4'-dithiodimorpholine (103-34-4) → N-(chlorosulfanyl)morpholine (2958-89-6)

Conditions	Yield
With sulfuryl dichloride In benzene at 5 - 33℃; for 0.283333h;	87.9%
With sulfuryl dichloride In tetrachloromethane at 60℃; for 2h;	85%
With chlorine In tetrachloromethane at 0 - 5℃;	48%

4,4'-dithiodimorpholine (103-34-4) + chromium(0) hexacarbonyl (199620-14-9, 13007-92-6) → Cr(CO)5(O(CH2CH2)2NSSN(CH2CH2)2O) (136921-41-0)

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); under purified nitrogen; irradn. of Cr(CO)6 for 90 min at room temp.; addn. of S2(N(CH2CH2)2O)2, stirring for 1 h; removal of solvent in vacuo; sublimation of excess of Cr(CO)6; residue dissolved in n-hexane; filtration; concn.; elem. anal.;	80%

4,4'-dithiodimorpholine (103-34-4) → dimorpholinotrisulfide (16131-52-5)

Conditions	Yield
With tritylsulfenyl chloride In chloroform at 20℃; for 24h;	75%

p-toluene sulfinic acid (536-57-2) + 4,4'-dithiodimorpholine (103-34-4) → bis-(toluene-4-sulfonyl)-disulfane (5962-57-2) + SS-morpholino 4-toluene(dithioperoxo)sulfonate (84655-87-8)

Conditions	Yield
In dichloromethane for 2h; Ambient temperature;	A 7% B 62%

p-toluene sulfinic acid (536-57-2) + 4,4'-dithiodimorpholine (103-34-4) → morpholinium p-toluenethiosulfonate (72087-93-5) + SS-morpholino 4-toluene(dithioperoxo)sulfonate (84655-87-8)

Conditions	Yield
In dichloromethane for 2h; Ambient temperature;	A n/a B 62%

4,4'-dithiodimorpholine (103-34-4) → morpholinosulfur trifluoride (51010-74-3)

Conditions	Yield
With potassium fluoride; chlorine In acetonitrile at 10 - 20℃; for 5.5h;	60%

2-thioxo-3H-1,3-benzothiazole (149-30-4) + 4,4'-dithiodimorpholine (103-34-4) → 2-morpholin-4-yldisulfanyl-benzothiazole (95-32-9)

Conditions	Yield
With ethanol

4,4'-dithiodimorpholine (103-34-4) + carbon oxide sulfide (463-58-1) → bis-(morpholine-4-carbonyl)-trisulfane

Conditions	Yield
With benzene

4,4'-dithiodimorpholine (103-34-4) + methyl thioisocyanate (556-61-6) → N-methyl-morpholine-4-carbonimidic acid thio anhydride

Conditions	Yield
With benzene at 140℃; unter vermindertem Druck;

4,4'-dithiodimorpholine (103-34-4) + para-thiocresol (106-45-6) → di-(4-tolyl)-tetrasulfide (25769-92-0)

Conditions	Yield
With ethanol

2-methyl-2,3-dihydro-[1,4]dithiino[2,3-c]pyrrole-5,7-dione (56342-50-8) + 4,4'-dithiodimorpholine (103-34-4) → 2-methyl-6-morpholin-4-ylsulfanyl-2,3-dihydro-[1,4]dithiino[2,3-c]pyrrole-5,7-dione (62582-70-1)

Conditions	Yield
With pyridine; silver nitrate In methanol

2-phenyl-2,3-dihydro-[1,4]dithiino[2,3-c]pyrrole-5,7-dione (35919-88-1) + 4,4'-dithiodimorpholine (103-34-4) → 6-morpholin-4-ylsulfanyl-2-phenyl-2,3-dihydro-[1,4]dithiino[2,3-c]pyrrole-5,7-dione (62582-69-8)

Conditions	Yield
With pyridine; silver nitrate In methanol

4,4'-dithiodimorpholine (103-34-4) + phenyl isothiocyanate (103-72-0) → morpholine-4-carbothioic acid N-morpholin-4-yldisulfanyl-anilide (36930-74-2)

Conditions	Yield
In toluene

4,4'-dithiodimorpholine (103-34-4) + acrylonitrile (107-13-1) → 3-morpholin-4-ylsulfanyl-propionitrile + 3,3'-thiobis-propanenitrile (111-97-7)

Conditions	Yield
(i) Li, liq. NH3, (ii) /BRN= 605310/; Multistep reaction;

4,4'-dithiodimorpholine (103-34-4) + methyl iodide (74-88-4) → 4-methyldisulfanyl-morpholine + 1-(methylthio)morpholine (4837-30-3)

Conditions	Yield
(i) Li, liq. NH3, (ii) /BRN= 969135/; Multistep reaction;

morpholine (110-91-8) + 4,4'-dithiodimorpholine (103-34-4) → N,N'-thiodimorpholine (5038-11-9) + N-4-thiamorpholine

Conditions	Yield
at 70 - 80℃;

4,4'-dithiodimorpholine (103-34-4) + 3-bromo-1,1,1-trifluoroacetone (431-35-6) → 1,1,1-Trifluoro-3-morpholin-4-yl-3-thioxo-propan-2-one (132288-68-7)

Conditions	Yield
With morpholine 1.) DMF, 10 min, 100 deg C 2.) DMF, 20 deg C, 30 min; Yield given. Multistep reaction;

4,4'-dithiodimorpholine (103-34-4) + cyclohexylamine (108-91-8) → N-4-thiamorpholine + N-Cyclohexyl-S-morpholin-4-yl-thiohydroxylamine

Conditions	Yield
at 70 - 80℃;

4,4'-dithiodimorpholine (103-34-4) + diethylamine (109-89-7) → N-4-thiamorpholine + N,N-Diethyl-S-morpholin-4-yl-thiohydroxylamine

Conditions	Yield
at 70 - 80℃;

4,4'-dithiodimorpholine (103-34-4) + carbon monoxide (201230-82-2) + benzyl bromide (100-39-0) → morpholine-4-carbothioic acid S-benzyl ester (56368-47-9)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene 1.) 1 atm, r.t.; Yield given. Multistep reaction;

4,4'-dithiodimorpholine (103-34-4) + carbon monoxide (201230-82-2) + allyl bromide (106-95-6) → Morpholine-4-carbothioic acid S-allyl ester

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene 1.) 1 atm, r.t.; Yield given. Multistep reaction;

Upstream product

• 110-91-8 morpholine 
• 5038-11-9 N,N'-thiodimorpholine 
• 139558-39-7 morpholino dithionitrite 
• 53402-10-1 thiocamphor 

Downstream Products

• 25769-92-0 di-(4-tolyl)-tetrasulfide 
• 52049-33-9 N-Morpholino-N'-phthalimidylsulfid 
• 51010-74-3 morpholinosulfur trifluoride 
• 72087-93-5 morpholinium p-toluenethiosulfonate 
• 84655-87-8 SS-morpholino 4-toluene(dithioperoxo)sulfonate 
• 5962-57-2 bis-(toluene-4-sulfonyl)-disulfane 
• 95-32-9 2-morpholin-4-yldisulfanyl-benzothiazole 
• 56368-47-9 S-benzyl morpholine-4-carbothioate 
• 111-97-7 3,3'-thiobis-propanenitrile 
• 36930-74-2 morpholine-4-carbothioic acid N-morpholin-4-yldisulfanyl-anilide 
• 62582-69-8 6-morpholin-4-ylsulfanyl-2-phenyl-2,3-dihydro-[1,4]dithiino[2,3-c]pyrrole-5,7-dione 

Relevant articles and documents

A new method for the synthesis of N,N′-thiobisamines

Reaction of secondary amines (morpholine and piperidine) with sulfur and iodine afforded N,N′-thiobisamines in good yields.

Method for synthesizing 4,4'-dithiodimorpholine

The invention discloses a method for synthesizing 4,4'-dithiodimorpholine. Sulfur monochloride and morpholine are used as raw materials, anhydrous trisodium phosphate is used as an acid binding agent,the sulfur monochloride and morpholine are reacted to produce 4,4'-dithiodimorpholine and hydrochloric acid, and the anhydrous trisodium phosphate can react with the hydrochloric acid generated in the reaction to avoid the hydrochloric acid with from reacting morpholine and the morpholine from losing the reactivity. The acid binding agent anhydrous trisodium phosphate is added in the method of the invention, so the dosage of the raw material morpholine is reduced, and the production cost is saved; and the product and impurities can be separated by washing with water after the reaction is finished, so the method has the advantages of simple production, high operability, simplicity in post-treatment and industrial application values. The appearance of the obtained product is a white needlecrystal, the yield is 90% or above, the purity is 98% or above, and use requirements are met.

Design, synthesis, and insecticidal activities of new N-benzoyl-N'-phenyl- N'-sulfenylureas

Aseries of new N'-alkylaminothio,N'-arylaminothio (or dithio), and N',N'-thio (or dithio) derivatives ofN'-benzoyl-N'-phenylureas were designed and synthesized as insect-growth regulators with sulfur dichloride or disulfur dichloride as the original reactant. The new compounds were identified by 1H nuclear magnetic resonancee (NMR) spectroscopy, elemental analysis [or high-resolution mass spectrometry (HRMS)], and single-crystal X-ray diffraction analysis. The X-ray results demonstrated that there exist N-S-N or N-S-S-N bonds in these new compounds. In comparison to the parent N-benzoyl-N'-phenylureas, these derivatives displayed better solubility. The insecticidal activities of the target compounds were evaluated. The results of bioassays showed that compounds 1-24 retained the larvicidal activities of the corresponding benzoylphenylureas (BPUs) and some compounds exhibited better larvicidal activities against oriental armyworm and mosquitoes than the parent BPUs. The larvicidal activities of the selected target compounds 1 and 24 against diamondback moth were better than that of the corresponding parent compounds E and triflumuron.