Methylamine → HCID 53848828, compound

HRID 2419077Notes

Reaction equation

HRID 2419077 reaction equation
[NH2:1][C:2]1SC(CO)=N[N:6]=1.CSC(=NC#N)SC.[NH2:17][CH2:18][CH2:19][S:20][CH2:21][C:22]1[C:27]([Br:28])=[CH:26][CH:25]=[CH:24][N:23]=1.CN.Br.Br.NCCSC[C:38]1C(Br)=CC=[CH:40][N:39]=1>C(O)C>[C:2]([NH:6][C:40]([NH:17][CH2:18][CH2:19][S:20][CH2:21][C:22]1[C:27]([Br:28])=[CH:26][CH:25]=[CH:24][N:23]=1)=[N:39][CH3:38])#[N:1]

Participants

7

Reactant 5

HCID 6329MethylamineHCID 66289Dimethyl N-cyanodithioiminocarbonateHCID 11062424(5-Amino-1,3,4-thiadiazol-2-yl)methanolHCID 129515272-{[(3-Bromopyridin-2-yl)methyl]sulfanyl}ethan-1-amineHCID 20316746HCID 20316746, compound

Product 1

HCID 53848828HCID 53848828, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution sodium nitrite (2.28 g) in water (10 ml) was added dropwise to a stirred mixture of 3-amino-2-hydroxymethylpyridine (4.8 g) in aqueous hydrobromic acid (48%, 10 ml) and water (5 ml) at 0.5° C. This solution of the diazonium salt was added to a hot solution of cuprous bromide (2.5 g) in 60% hydromic acid and following cessation of nitrogen evolution the mixture was heated on the steam bath for 0.5 hours, diluted with water and saturated with hydrogen sulphide. Filtration, concentration to low bulk and extraction with chloroform yielded 3-bromo-2-hydroxymethylpyridine (4.8 g). This was dissolved in aqueous hydrobromic acid (48%, 50 ml), cysteamine hydrochloride (3.22 g) added and the solution obtained was heated under reflux for 6 hours. Concentration, followed by recrystalliation from aqueous ethanol afforded 2-((2-aminoethyl)thiomethyl)-3-bromopyridine dihydrobromide (6.1 g), m.p. 252°-254°. (Found: C, 23.7; H, 3.4; N, 6.7; S, 7.9; C8H11Br N2S.2HBr. requires: C, 23.5; H, 3.2; N, 6.9; S, 7.8). (ii) Sequential reaction of dimethylcyanodithioimidocarbonate with 2-((2-aminoethyl)thiomethyl)-3-bromopyridine) and excess methylamine at room temperature in ethanol, the methylamine being added after initial standing overnight and the solution then allowed to stand for a further four hours, followed by chromatographic purification on a column of silica gel with elution by ethyl acetate and final recrystallisation from ethyl acetate-petroleum ether gave N-cyano-N'-[2-((3-bromo-2-pyridyl)methylthio)ethyl]-N"-methylguanidine m.p. 114°-116°. (Found: C, 40.6; H, 4.4; N, 21.4; S, 9.8. C11H14Br N5S. requires: C, 40.3; H, 4.3; N, 21.3; S, 9.8).

Workup

  1. waitto stand for a further four hours
  2. customfollowed by chromatographic purification on a column of silica gel with elution by ethyl acetate
  3. customfinal recrystallisation from ethyl acetate-petroleum ether

Sources & evidence

ORD record
ord-e434191e437040d3aaafaaaaa1082615
Source dataset
uspto-grants-1978_08
Patent number
US04104382

Reaction notes

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