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[ CAS No. 4478-93-7 ] {[proInfo.proName]}

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Chemical Structure| 4478-93-7
Chemical Structure| 4478-93-7
Structure of 4478-93-7 * Storage: {[proInfo.prStorage]}
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Product Details of [ 4478-93-7 ]

CAS No. :4478-93-7 MDL No. :MFCD00198068
Formula : C6H11NOS2 Boiling Point : -
Linear Structure Formula :- InChI Key :SUVMJBTUFCVSAD-UHFFFAOYSA-N
M.W : 177.29 Pubchem ID :5350
Synonyms :
SFN

Calculated chemistry of [ 4478-93-7 ]

Physicochemical Properties

Num. heavy atoms : 10
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.83
Num. rotatable bonds : 5
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 48.4
TPSA : 80.73 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.38 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.11
Log Po/w (XLOGP3) : 1.41
Log Po/w (WLOGP) : 2.11
Log Po/w (MLOGP) : 1.84
Log Po/w (SILICOS-IT) : 2.16
Consensus Log Po/w : 1.93

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.5
Solubility : 5.64 mg/ml ; 0.0318 mol/l
Class : Very soluble
Log S (Ali) : -2.71
Solubility : 0.346 mg/ml ; 0.00195 mol/l
Class : Soluble
Log S (SILICOS-IT) : -2.1
Solubility : 1.41 mg/ml ; 0.00796 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 3.07

Safety of [ 4478-93-7 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P501-P261-P270-P210-P271-P264-P280-P302+P352-P370+P378-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P310+P330-P304+P340+P311-P403+P233-P403+P235-P405 UN#:2810
Hazard Statements:H301+H331-H315-H319-H335-H227 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 4478-93-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 4478-93-7 ]

[ 4478-93-7 ] Synthesis Path-Downstream   1~86

  • 1
  • [ 4478-93-7 ]
  • [ 62-53-3 ]
  • [ 7431-79-0 ]
  • 2
  • 4-methylsulfinylbutyl glucosinolate [ No CAS ]
  • [ 2280-44-6 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
With myrosinase; buffer pH = 6.5 at 37℃;
  • 3
  • [ 4478-93-7 ]
  • [ 289-16-7 ]
  • [ 2949-92-0 ]
  • [ 13882-12-7 ]
  • [ 51598-96-0 ]
YieldReaction ConditionsOperation in experiment
With water at 50℃;
  • 5
  • sulforaphane-cysteine [ No CAS ]
  • [ 52-90-4 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
In water; dimethyl sulfoxide at 37℃;
  • 6
  • C11H20N2O5S3 [ No CAS ]
  • [ 4478-93-7 ]
  • N-acetyl-L-cysteine [ No CAS ]
YieldReaction ConditionsOperation in experiment
In water; dimethyl sulfoxide at 37℃;
  • 7
  • (11R,16S)-16-amino-11-((carboxymethyl)carbamoyl)-13-oxo-8-methylsulfinyl-2,9-dithia-7,12-diazaheptadecan-17-oic acid [ No CAS ]
  • [ 4478-93-7 ]
  • [ 70-18-8 ]
YieldReaction ConditionsOperation in experiment
In water; dimethyl sulfoxide at 37℃;
  • 8
  • [ 463-71-8 ]
  • [ 84104-30-3 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
85.7% With sodium hydroxide In chloroform; water for 1h; 1 A one liter round bottom flask equipped with a stir bar was charged with Intermediate D (10.8 g, 79.9 mmol, 1.00 eq.), 300 mL of chloroform, and 133 mL of 1N NaOH (aq) olution (132.8 mmol, 1.66 eq.). To the biphasic solution, thiophosgene (13.78 g, 119.8 mmol, 1.50 eq.) was charged. The reaction was stirred vigorously for one hour before an aliquot was checked by thin layer chromatography. The mixture was diluted with 300 mL chloroform and 200 mL brine. The organics were removed and aqueous re-extracted with 2×500 mL chloroform. The organics were combined, dried over sodium sulfate, and concentrated. The residue was adsorbed onto 20 g silica and columned over 50 g silica, eluting with 0 to 4% methanol in chloroform. 12.14 grams (85.7% yield) of the desired product was collected as a light yellow oil.
57% With sodium hydroxide In chloroform for 0.583333h;
52% With sodium hydroxide In chloroform at 20℃; for 1h;
With sodium hydrogencarbonate In dichloromethane

  • 9
  • [ 4478-93-7 ]
  • [ 616-91-1 ]
  • N-acetyl-S-{N-[4-(methylsulfinyl)butyl]thiocarbamoyl}-L-cysteine [ No CAS ]
YieldReaction ConditionsOperation in experiment
69.5% With sodium hydrogencarbonate In ethanol; water
36% With sodium hydroxide In ethanol; water at 23℃; for 2h; N-acetyl-S-(((methylsulfinyl)butyl) carbamothioyl)-L-cysteine (27) To a solution of acetyl-L-cysteine (92 mg, 0.564 mmol) in ethanol (2 mL) and water (2 mL), wasadded 1 M aq. NaOH to adjust pH to 7-8, then 1-isothiocyanato-4-(methylsulfinyl)butane (100mg, 0.564 mmol) in Ethanol (2.000 mL) and the resulting mixture was stirred at 23 °C for 2 h,the solvent was evaporated. The crude product was purified on a Gilson HPLC (YMC C18 5mm/12 nm 50 x 20 mm preparatory column), eluting at 20 mL/min with a linear gradient runningfrom water to acetonitrile. The desired fractions were concentrated to afford N-acetyl-S-(((methylsulfinyl)butyl) carbamothioyl)-L-cysteine (27) (69 mg, 36%).
  • 10
  • [ 4430-36-8 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
100% With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 0.5h;
100% With dihydrogen peroxide In methanol
95% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -5℃; for 3h; 1.5 (5) Preparation of sulforaphane (1-isothiocyanato-4-methylsulfinylbutane, compound 5) Weigh 2.42 g (15 mmol) of 1-isothiocyanato-4-methylthiobutane into a 200 mL round bottom flask,Was added 50 mL of anhydrous dichloromethane dissolved, the mixed solution was cooled to -5 ° C in an ice bath,After cooling for 5 minutes, a solution of 2.85 (16.5 mmol) m-chloroperbenzoic acid in dichloromethane (10 mL) was slowly added dropwise with a constant pressure dropping funnel and the reaction was continued while the addition was The addition was complete to maintain the reaction temperature for 3 hours, the reaction was quenched with 30 mL of saturated sodium bicarbonate solution and extracted with dichloromethane (30 mL × 2). The organic phases were combined and washed with saturated brine and dried over anhydrous sodium sulfate. Dichloromethane was removed under reduced pressure and passed through a plug of flash silica gel2.52 g (95%) of purified sulforaphane (Compound 5) was purified.
92.5% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -10 - -2℃; for 1h; 1.3 Synthesis of 1-isothiocyanato-4-methylsulfinylbutane A 250 mL round bottom flask reactor was placed in a fume hood and 2.42 g (15 mmol) of 1-isothiocyanato-4-methylthiobutane was weighed into a reactor. 50 mL of methylene chloride was added and the round bottom The flask reactor was cooled to -10 ° C in an ice-salt bath and then a mixed solution of 2.74 g (15.9 mmol) of m-chloroperbenzoic acid (m-CPBA) and 50 mL of dichloromethane was added dropwise to the reactor and the reaction The temperature between -5 ~ -2 , after the drop is completed, continue to -5 ~ -2 between the reaction 1h, then add 100mL saturated sodium bicarbonate solution to terminate the reaction. After completion of the reaction, the organic phase was separated and the aqueous phase was extracted three times with 50 mL of dichloromethane. The combined dichloromethane phases were washed with saturated sodium bicarbonate solution and saturated sodium chloride solution, respectively, and then dried. The initial product was purified by silica gel column chromatography to give 2.46 g of product (compound 6) in a yield of 92.5%. The compound 6 was then placed at low temperature for preservation.GC and LC-MS analysis showed that the purity of the product was greater than 99.3%
91% With dihydrogen peroxide; acetic acid at 20℃; for 1h; Green chemistry; 3.4. Sulforaphane A 30% solution of hydrogen peroxide (8 mmol) wasslowly added to 4 (2 mmol) and glacial acetic acid (2 mL).The reaction mixture was then stirred at room temperature in1 hour. The resulting solution was neutralized with aqueousNaOH (4 M) and the product was extracted with dichloromethane(3 15 mL). The dichloromethane layer was driedover anhydrous Na2SO4 and the solvent was removed undervacuum to give 0,32 g sulforaphane (yield: 91%).
91% With dihydrogen peroxide; acetic acid at 20℃; for 1h; 3.4. Sulforaphane A 30% solution of hydrogen peroxide (8 mmol) wasslowly added to 4 (2 mmol) and glacial acetic acid (2 mL).The reaction mixture was then stirred at room temperature in1 hour. The resulting solution was neutralized with aqueousNaOH (4 M) and the product was extracted with dichloromethane(3 15 mL). The dichloromethane layer was driedover anhydrous Na2SO4 and the solvent was removed undervacuum to give 0,32 g sulforaphane (yield: 91%).
90% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1.41667h;
85% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -10 - 0℃; for 1.08333h; 1 5.1.6 General procedures for preparation of 77-97 General procedure: A solution of isothiocyanate 56-76 (3 mmol) in CH2Cl2 (20 mL) was chilled to-10°C in an ice-salt bath. A solution of 85% MCPBA (3 mmol) in CH2Cl2 (10mL) was added dropwise over 5 min, while the internal temperature was kept below 0°C. When the addition was completed, the mixture was stirred at 0°C for 1 h, and then the resulting light-yellow suspension was treated with saturated NaHCO3 (15 mL). The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (2×15 mL). The combined CH2Cl2 layers were washed with saturated NaHCO3 (30 mL) and brine (30 mL), then dried with anhydrous MgSO4 and concentrated with a rotary evaporator. The crude product was purified by flash chromatography (MeOH:CH2Cl2=1:20) to give a light-yellow oil 77-97.
84% With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Compound 13; l-isothiocyanato-4-(methylsulfinyl)butane (trivial name D,L- sulforaphane); The following procedure was adapted from that previously reported by Vermeulen, et al (25) Compound 12 (795 mg, 4 930 mmols) was dissolved in anhydrous CH2Cl2 (7 0 mL) under argon To this was slowly added a solution of m- CPBA (934 mg, 5 410 mmols) in anhydrous CH2Cl2 (6 25 mL) After 2 h, the reaction was diluted with CH2Cl2 and the organics were washed with sat'd NaHCO3, brine, and dried over Na2SO4 prior to concentration in vacuo Silica gel chromatography (2 1 CH2Cl2 CH3 CN) and subsequent concentration afforded 735 mg 13 as a light yellow oil (84% yield) 1H NMR (CDCl3) δ 3 58 (t, J = 6 2 Hz, 2H), 2 71 (m, 2H), 2 58 (s, 3H), 1 95-1 81 (m, 4H) 13C NMR (CDCl3) δ 129 8, 52 9, 44 3, 38 3, 28 5, 19 6 HRMS (ESI- EMM) calc'd for [M + Na]+ m/z 200 0180, found 200 0172
84% With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Inert atmosphere; Compound 13 Compound 13: 1-isothiocyanato-4-(methylsulfinyl)butane (trivial name: D,L-sulforaphane). The following procedure was adapted from that previously reported by Vermeulen, et al. (25). Compound 12 (795 mg, 4.930 mmols) was dissolved in anhydrous CH2Cl2 (7.0 mL) under argon. To this was slowly added a solution of m-CPBA (934 mg, 5.410 mmols) in anhydrous CH2Cl2 (6.25 mL). After 2 h, the reaction was diluted with CH2Cl2 and the organics were washed with sat'd. NaHCO3, brine, and dried over Na2SO4 prior to concentration in vacuo. Silica gel chromatography (2:1 CH2Cl2:CH3CN) and subsequent concentration afforded 735 mg 13 as a light yellow oil (84% yield). 1H NMR (CDCl3) δ 3.58 (t, J=6.2 Hz, 2H), 2.71 (m, 2H), 2.58 (s, 3H), 1.95-1.81 (m, 4H). 13C NMR (CDCl3) δ 129.8, 52.9, 44.3, 38.3, 28.5, 19.6. HRMS (ESI-EMM) calc'd for [M+Na]+m/z 200.0180. found 200.0172.
77% With 3-chloro-benzenecarboperoxoic acid In dichloromethane
73% With phosphoric acid; oxygen; uranyl(VI) acetate dihydrate In water; acetonitrile at 20℃; for 12h; Schlenk technique; Irradiation;
Stage #1: erucin With alpha cyclodextrin In water at 0℃; for 0.5h; Inert atmosphere; Stage #2: With dihydrogen peroxide In water Cooling with ice; 1 Example 1- Preparation of sulforaphane {1-isothiocyanato-4-methylsulfinylbutane) A 5-L multi-neck round bottom flask equipped with an overhead stirrer, a temperatureprobe and a 500mL addition funnel was set-up with a positive flow of N2. a-Cyclodextrin (30g,0.03 moles, 0.01 equivalents) was dissolved in 1 L of distilled water and degassed over 30minutes by purging with nitrogen. To the above solution was added 50lg (3.1 moles, 1 equivalent) of 1-isothiocyanato-4-methylthiobutane (Formula A) and degassed again at 0 °C over30 minutes. To this biphasic reaction mixture was added 305 mL of H20 2 (3.1 moles, 1equivalent, 35% aq.) slowly while maintaining temperature between 0-2°C [NOTE: Peroxidewas dropped in at a rate sufficiently low so that the temperature did not increase above l0°C].Once the addition complete, the reaction mixture was stirred at ice bath temperature for about 8 hours and then slowly allowed to come to room temperature overnight. Reaction mixture wasfiltered to remove the light yellow insoluble solids and then the filtrate was kept in therefrigerator for -lh. Based on the analytical HPLC the crude sulforaphane was -95% pure.20[00103] This material was used for the complexation step (Example 2) without any furtherworkup/purification. All three batches were conducted at the same reaction scale and the reactions proceeded in similar way in terms of reaction time and product purity. 1HNMR (CDCh, 400 MHz); 81.90 (m, 4H), 2.58 (s, 3H), 2.75 (m, 2H), 3.60 (t, 2H). 13 CNMR (CDCh, 100 MHz); us: l30.2, 53.4, 44.5, 38.5, 29.5, 20.1

Reference: [1]Vermeulen, Martijn; Zwanenburg, Binne; Chittenden, Gordon J.F.; Verhagen, Hans [European Journal of Medicinal Chemistry, 2003, vol. 38, # 7-8, p. 729 - 737]
[2]Location in patent: experimental part Papi, Alessio; Orlandi, Marina; Bartolini, Giovanna; Barillari, Jessica; Iori, Renato; Paolini, Moreno; Ferroni, Fiammetta; Fumo, Maria Grazia; Pedulli, Gian Franco; Valgimigli, Luca [Journal of Agricultural and Food Chemistry, 2008, vol. 56, # 3, p. 875 - 883]
[3]Current Patent Assignee: WUHAN POLYTECHNIC UNIVERSITY - CN107311902, 2017, A Location in patent: Paragraph 0017
[4]Current Patent Assignee: BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY - CN105001135, 2017, B Location in patent: Paragraph 0015; 0022; 0032; 0034-0036
[5]Vo, Duy-Viet; Truong, Van-Dat; Tran, Thanh-Dao; Do, Van-Thanh-Nhan; Pham, Ngoc-Tuan-Anh; Thai, Khac-Minh [Letters in Organic Chemistry, 2016, vol. 13, # 1, p. 7 - 10]
[6]Vo, Duy-Viet; Truong, Van-Dat; Tran, Thanh-Dao; Do, Van-Thanh-Nhan; Pham, Ngoc-Tuan-Anh; Thai, Khac-Minh [Letters in Organic Chemistry, 2016, vol. 13, # 1, p. 7 - 10]
[7]Location in patent: experimental part Chen, Xin; Li, Zhengyi; Sun, Xiaoqiang; Ma, Hongzhao; Chen, Xiaoxin; Ren, Jie; Hu, Kun [Synthesis, 2011, # 24, p. 3991 - 3996]
[8]Hu, Kun; Qi, Yan-Jie; Zhao, Juan; Jiang, He-Fei; Chen, Xin; Ren, Jie [European Journal of Medicinal Chemistry, 2013, vol. 64, p. 529 - 539]
[9]Current Patent Assignee: WARF (in: University of Wisconsin); UNIVERSITY OF WISCONSIN SYSTEM - WO2008/8954, 2008, A2 Location in patent: Page/Page column 24
[10]Current Patent Assignee: Rajski, Scott R.; Mays, Jared Rae - US2013/116203, 2013, A1 Location in patent: Paragraph 0092
[11]Ganin, Hadas; Rayo, Josep; Amara, Neri; Levy, Niva; Krief, Pnina; Meijler, Michael M. [MedChemComm, 2013, vol. 4, # 1, p. 175 - 179]
[12]Li, Yiming; Rizvi, S. Aal-e-Ali; Hu, Deqing; Sun, Danwen; Gao, Anhui; Zhou, Yubo; Li, Jia; Jiang, Xuefeng [Angewandte Chemie - International Edition, 2019, vol. 58, # 38, p. 13499 - 13506][Angew. Chem., 2019, vol. 131, # 38, p. 13633 - 13640,8]
[13]Current Patent Assignee: ZHEJIANG JIUZHOU PHARMACEUTICAL CO., LTD. - WO2013/179057, 2013, A1 Location in patent: Paragraph 00102; 00103; 00104; 00105; 00106
  • 11
  • 4-methylsulfinylbutyl glucosinolate [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
With phosphate buffer; myrosinase at 37℃;
  • 12
  • [ 4478-93-7 ]
  • [ 504-84-7 ]
YieldReaction ConditionsOperation in experiment
66% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -20 - 20℃; for 3h; Inert atmosphere; 15 Oxidation of Sulforaphane EXAMPLE 15 Oxidation of Sulforaphane 1.77 g of sulforaphane (1 equivalent) obtained in Example 4, as well as 15 mL of dichloromethane are introduced into the reactor, and the mixture is then degassed and set under nitrogen. 1.6 equivalents of meta-chloroperbenzoic acid solubilized in 25 mL of dichloromethane are placed in an isobaric dropping funnel and poured dropwise (within 20 mins) at room temperature, into the reactor. The addition causes exothermy for producing oxidized sulforaphane i.e. 1-isothiocyanato-4-(methylsulfonyl)butane or 4-methylsulfonylbutyl-isothiocyanate, Stirring is maintained for 2 hours at room temperature. A white precipitate forms. After this period, the reactor is cooled to -20° C. and maintained for 1 hour at this temperature before carrying out filtration. The filtrate and the solid are analyzed by NMR. The solid contains derivatives of MCPBA, while the filtrate contains the oxidized product, as well as a few traces of aromatic residues and of residual sulforaphane. The product is washed with a minimum of a solution saturated with NaHCO3 in order to remove the benzoic acid, and then chromatographed on silica gel, eluent CH2Cl2 100% and then AcOEtT 100%. After evaporation of the solvents, 1.27 g of a yellowish liquid which solidifies are obtained with a yield of 66%. TLC: Eluent: AcOEt 100%; Developer: phosphomolybdic acid;[0261] Rf=0.5. [0262] 1H NMR (300 MHz; CDCl3): [0263] δ (ppm): 3.61 (t, 2H, -CH2-NCS); 3.07 (t, 2H, -S(O)2-CH2); 2.94 (s, 3H, CH3-S(O)2-); 2.07-1.85 (m, 4H, -CH2-CH2-). [0264] 13C NMR (75 MHz; CDCl3): [0265] δ (ppm): 53.63; 44.44; 40.74; 28.55; 19.79. [0266] UV spectrum: [0267] λmax=245 nm [0268] Melting point: 58° C.
60% With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Compound 14; l-isothiocyanato-4-(methylsulfonyl)butane (trivial name erysolin); The following procedure was adapted from that previously reported by Vermeulen, et al (25) Compound 12 (283 mg, 1 754 mmols) was dissolved in anhydrous CH2Cl2 (2 5 mL) under argon To this was slowly added a solution of m- CPBA (964 mg, 5 586 mmols) in anhydrous CH2Cl2 (5 0 mL) After 2 h, the reaction was diluted with CH2Cl2 and the organics were washed with sat'd NaHCO3, brine, and dried over Na2SO4 prior to concentration in vacuo Silica gel chromatography (CH2Cl2) and subsequent concentration afforded 203 mg 14 as an off-white solid (60% yield) 1H NMR (CDCl3) δ 3 56 (t, J = 6 1 Hz, 2H), 3 01 (t, J = 7 8 Hz, 2H), 2 86 (s, 3H), 1 90 (m, 2H), 1 81 (m, 2H) 13C NMR (CDCl3) δ 130 4, 53 5, 44 4, 40 6, 28 4, 19 6 HRMS (EI- EMM) calc'd for [M]+ m/z 193 0231, found 193 0230
  • 13
  • [ 55021-77-7 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 12.5 mmol / sodium hydroxide / CHCl3 2: 100 percent / m-chloroperbenzoic acid / CH2Cl2 / 0.5 h
Multi-step reaction with 2 steps 1: 64 percent / aq. H2O2; H2SO4; i-PrOH / methanol / 2 h / 20 °C 2: 57 percent / aq. NaOH / CHCl3 / 0.58 h
Multi-step reaction with 2 steps 1: sulfuric acid; dihydrogen peroxide / methanol; water; isopropyl alcohol / 3 h / 20 °C 2: sodium hydroxide / chloroform / 1 h / 20 °C
Multi-step reaction with 2 steps 1.1: triethylamine / tetrahydrofuran / 0 - 20 °C 1.2: 0.5 h / 0 - 20 °C 2.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.08 h / -10 - 0 °C
Multi-step reaction with 2 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C
Multi-step reaction with 2 steps 1: sodium hydroxide / dichloromethane / 3.5 h / 0 - 20 °C / Inert atmosphere 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 2 h / Inert atmosphere

  • 14
  • [ 52096-68-1 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 21.1 mmol / hydrazine monohydrate; hydrogen chloride / ethanol / 2 h / 75 °C 2: 12.5 mmol / sodium hydroxide / CHCl3 3: 100 percent / m-chloroperbenzoic acid / CH2Cl2 / 0.5 h
Multi-step reaction with 3 steps 1.1: hydrazine hydrate / methanol / 70 °C 2.1: triethylamine / tetrahydrofuran / 0 - 20 °C 2.2: 0.5 h / 0 - 20 °C 3.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.08 h / -10 - 0 °C
Multi-step reaction with 3 steps 1: hydrazine hydrate / ethanol / 3 h / Reflux 2: sodium hydroxide / dichloromethane / 3.5 h / 0 - 20 °C / Inert atmosphere 3: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 2 h / Inert atmosphere
Multi-step reaction with 3 steps 1: acetic acid; dihydrogen peroxide 2: hydrazine hydrate / ethanol / Reflux 3: sodium hydrogencarbonate / dichloromethane

  • 15
  • [ 59121-24-3 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 63 percent / BH3 / tetrahydrofuran / 20 °C 2: 64 percent / aq. H2O2; H2SO4; i-PrOH / methanol / 2 h / 20 °C 3: 57 percent / aq. NaOH / CHCl3 / 0.58 h
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / diethyl ether / 0.5 h / Reflux 2: sulfuric acid; dihydrogen peroxide / methanol; water; isopropyl alcohol / 3 h / 20 °C 3: sodium hydroxide / chloroform / 1 h / 20 °C
Multi-step reaction with 3 steps 1.1: lithium aluminium tetrahydride / diethyl ether / 3 h / Inert atmosphere; Reflux 2.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 3.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 3.2: 2.25 h / 0 - 20 °C
  • 16
  • [ 463-71-8 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 4-(methylthio)-1-butylamine With dihydrogen peroxide In water; acetone at 50℃; Stage #2: thiophosgene With sodium hydroxide In dichloromethane; water; acetone for 0.5h; 1 Dissolve 40 g of 4-chlorobutyronitrile (ref. Aldrich C 3,000-0) in 800 ml of absolute ethanol previously distilled over sodium. Then add 27 g of methane thioate (ref. Fluka 71742) and stir for 15 hours at 25° C. Filter the suspension on paper and evaporate under reduced pressure. Absorb in 400 ml of ethyl ether. Filter again on paper. An ethereal solution is obtained containing 32 g of raw 4-methylthiobutyronitrile. Prepare a suspension of 25 g of lithium-aluminium hydride in 400 ml of ethyl ether. Add the solution of 4-methylthiobutyronitrile gradually to the suspension of lithium-aluminium hydride, then reflux for 2 h 30 min. Then neutralize the suspension by slowly adding, under reflux, 80 ml of distilled water. When boiling ceases, add 120 ml of distilled water to complete the neutralization of any hydride that remains. Filter on a glass frit. Wash the insoluble matter on the filter with 200 ml of ethyl ether. Combine the ethereal fractions and evaporate to dryness. 26.9 g of methylthiobutylamine is obtained. Absorb the product obtained in 80 ml of acetone, and then add, a little at a time, 23 ml of 35% hydrogen peroxide. Leave over night on a water bath at 50° C. Then add a small amount of activated charcoal, filter and slowly add 200 ml of chloroform containing 20 ml of thiophosgene, then 300 ml of an aqueous solution of sodium hydroxide at 5%. Leave to act for 30 min. Then extract the mixture in counter-current with 8 times 200 ml of dichloromethane. Collect the organic phase, dry over sodium sulphate and evaporate. Then redistill the residue at 135° C. under 7.10-2 torr. We obtain 12.5 g of D,L-sulphoraphane, the identity of which is verified by mass spectrometry.
  • 17
  • [ 4478-93-7 ]
  • N,N’-di-(4-methylsulfinylbutyl)thiourea [ No CAS ]
YieldReaction ConditionsOperation in experiment
43% With water for 24h; Heating / reflux; 1 Under an inert atmosphere, dilute 2 g (11 mmol) of sulphoraphane obtained above in 15 ml of water, then reflux the solution for 24 hours, protected from the light. At room temperature, concentrate the solution at reduced pressure and absorb the residue in dichloromethane for chromatography on a column of silica gel (eluent: CH2Cl2/CH3OH: 90/10) to give 1.70 g (5 mmol) of 1,3-bis-(5-methanesulphinylbutyl)-thiourea (bis MSiBT) as a colourless oil, at a yield of 43%. 1H NMR (300 MHz): 6.45 (d1, 2H, NH), 3.53 (t. H, J=6.0 Hz), 2.87 (m, 4H), 2.65 (s, 6H), 1.78 (m, 8H). 13C NMR (50.3 MHz): 24.0 (CH2), 32.1 (CH2), 41.2 (CH2-CH2), 47.2 (CH3), 57.4 (CH2SO), C (IV) not observed. IR (ν, cm-1): 2176, 2096, 1140, 940 cm-1. IC.MS m/z: 312 (MH+).
With water for 1h; Reflux; A single main non-volatile product was isolated and identified as being the coupling product of the amine generated during hydrolysis of sulforaphane on residual sulforaphane: N,N′-di-(4-methylsulfinyl)butyl thiourea 14. The formation of this product indeed results from the reaction of sulforaphane 1 with 4-methylsufinyl butylamine 15 itself generated by hydrolysis of sulforaphane 1 according to the reaction (III)
  • 18
  • [ 4478-93-7 ]
  • 1-(4-methylsulfinyl-butyl)-3-(4-methylsulfonyl-butyl)-thiourea [ No CAS ]
YieldReaction ConditionsOperation in experiment
12% With water; oxygen In dichloromethane for 24h; Heating / reflux; 2 Preparation of 1-(5-methanesulphinylbutyl)-3-(5-methanesulphonylbutyl)-thiourea Oxidation of just one of the two sulphur atoms of the sulphoraphane molecule was achieved by carrying out the reaction of example 1 of synthesis of 1,3-bis-(5-methanesulphinylbutyl)-thiourea in the open air, rather than under an inert atmosphere. Dilute 1 g (5.5 mmol) of sulphoraphane in 10 ml of water, then reflux the solution for 24 hours, protected from the light. At room temperature, concentrate the solution under reduced pressure and absorb the residue in dichloromethane for chromatography on a column of silica gel (eluent: CH2Cl2/CH3OH: 90/10) to give 200 mg of 1-(5-methanesulphinylbutyl)-3-(5-methanesulphonylbutyl)-thiourea (MSBMSBT) as a colourless oil, at a yield of 12%. 1H NMR (300 MHz): 6.55 (solid, 2H, NH), 3.55 (t, 4H, CH2), 3.15 (t, 2H, SO2CH2), 2,80 (t, 2H, SOCH2), 2.60 (s, 3H, SOCH3), 2.90 (s, 3H, SO2CH3), 1.80-1.87 (m, 8H, CH2). 13C NMR (50.3 MHz): 20.5 (CH2), 28.5 (CH2), 39.8 (CH3SO), 41.0 (CH3SO2), 43.5 (CH2-NH), 54.1 (CH2SO), 44.8 (CH2SO2), 183.35 (C=S). IR (ν, cm-1): 2176, 2096, 1140, 940 cm-1. IC.MS m/z: 328 (MH+).
  • 20
  • [ 4478-93-7 ]
  • L-lysine-[(13)C6(15)N2] hydrochloride [ No CAS ]
  • N6-([3-(methylsulfinyl)butyl]amino}carbonothioyl)[(13)C6(15)N2]lysine [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% Stage #1: L-lysine-[(13)C6(15)N2] hydrochloride With copper(II) carbonate; sodium hydroxide In water at 100℃; for 0.333333h; Stage #2: D,L-sulforaphane In 1,4-dioxane; water at 20℃; for 4h; Stage #3: With sodium sulfide In 1,4-dioxane; water at 20℃; for 0.166667h;
  • 21
  • [ 4478-93-7 ]
  • [ 1946-82-3 ]
  • C14H27N3O4S2 [ No CAS ]
  • 22
  • [ 1350472-27-3 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: hydrogenchloride / dichloromethane / 2 h / 20 °C 2.1: triethylamine / tetrahydrofuran / 1.5 h / 0 - 20 °C 2.2: 0.5 h / 0 - 20 °C 3.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.42 h / 0 °C
Multi-step reaction with 3 steps 1: hydrogenchloride / dichloromethane / 2 h / 20 °C 2: triethylamine / dichloromethane / 12 h / 0 - 20 °C 3: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.42 h / 0 °C
  • 23
  • 4-(methylsulfanyl)butan-1-amine hydrochloride [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: triethylamine / tetrahydrofuran / 1.5 h / 0 - 20 °C 1.2: 0.5 h / 0 - 20 °C 2.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.42 h / 0 °C
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 12 h / 0 - 20 °C 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1.42 h / 0 °C
  • 24
  • [ 84104-30-3 ]
  • [ 4478-93-7 ]
  • N,N’-di-(4-methylsulfinylbutyl)thiourea [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% In dichloromethane for 1h; Reflux; 9 Synthesis of 1,3-bis-(4-methlsulfinyl)-butyl)-thiourea EXAMPLE 9 Synthesis of 1,3-bis-(4-methlsulfinyl)-butyl)-thiourea 4.43 g of sulforaphane obtained in Example 4 (1 equivalent), are dissolved in 10 mL of dichloromethane and placed in an isobaric dropping funnel surmounting a reactor in which are placed 4.79 g of 4-methylsulfinylbutylamine (1.1 equivalents), as well as 40 mL of dichloromethane. The mixture is refluxed and maintained thus, with stirring for 1 hour. The solvent is then removed in the rotary evaporator, and the crude mixture is then taken up in dichloromethane added with hexane in order to obtain precipitation of the thiourea. The thereby obtained solid is milled, and then successively washed with diethyl ether and with hexane before being dried. 7.6 g of a white powder are finally obtained, i.e. a yield of 97%. TLC: Eluent: CH2Cl2-MeOH 8/2; Developer: phosphomolybdic acid or ninhydrin; 1H NMR (300 MHz; CDCl3): δ (ppm): 6.91 (broad s, 2H, -NH-); 3.54 (m, 4H, -CH2-NH-); 2.74 (t, J=7.2 Hz, 4H, S(O)-CH2-); 2.57 (s, 6H, CH3-S(O)-); 1.70-1.87 (m, 8H, -CH2-CH2-). 13C NMR (75 MHz; CDCl3):[0204] δ (ppm): 182.51; 53.60; 43.32; 38.49; 28.09; 19.98. [0205] UV spectrum: [0206] λmax=239 nm [0207] Melting point; 89° C.
  • 25
  • [ 75-15-0 ]
  • [ 84104-30-3 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
79% Stage #1: carbon disulfide; (+/-)-1-amino-4-(methylsulfinyl)butane With triethylamine In ethanol at 20℃; for 0.5h; Inert atmosphere; Stage #2: With dmap; di-<i>tert</i>-butyl dicarbonate In ethanol at 0 - 20℃; for 2.25h; 4 EXAMPLE 4 Synthesis of Sulforaphane EXAMPLE 4 Synthesis of Sulforaphane [0129] 18.39 g of 4-methylsulfinylbutylamine (1 equivalent), as well as 200 mL of absolute ethanol are introduced into a reactor, and the mixture is then stirred at room temperature, degassed and placed under nitrogen. [0130] 1 equivalent of triethylamine is then poured into the reactor, followed by 10 equivalents of carbon disulfide. The addition of CS2 is exothermic and has to be accomplished dropwise; the medium assumes a yellow coloration. [0131] The thereby formed mixture is maintained with stirring at room temperature for 30 mins before being cooled to 0° C. [0132] 0.99 equivalents of di-tert-butyl dicarbonate dissolved in 100 mL of absolute ethanol are then added via an isobaric dropping funnel within about 30 mins. By this same means, addition of 3 mol % of DMAP in solution in 50 mL of absolute ethanol follows. [0133] The reaction medium is then maintained with stirring and at 0° C. for 15 mins, and then the ice bath is removed and the reaction is continued for 2 hours at room temperature. [0134] The reaction crude mixture is transferred into a 1-neck flask and concentrated in the rotary evaporator and then taken up in 30 mL of dichloromethane in order to be filtered on charcoal. The filter is rinsed with dichloromethane and the collected filtrates are again placed in the rotary evaporator. 23.1 g of an orange oil are thereby obtained. [0135] The raw product essentially contains traces of residual DMAP. Purification on a chromatography column was initially considered but we may advantageously replace this by simple washing. [0136] This crude product is then taken up in 100 mL of dichloromethane in order to carry out acid washing. The obtained solution is then briefly stirred in the presence of 200 mL of 1N HCl. After decantation, the aqueous phase is again extracted once with dichloromethane, and the collected organic phases are washed with water, dried on MgSO4. The solvent is finally removed in the rotary evaporator. 21.12 g of a yellow (oily) liquid are thereby obtained, i.e. a yield of 88%. [0137] The overall yield of the reaction in 4 steps is therefore 79% which to our knowledge is well above all the yields described in the literature for the various routes for accessing sulforaphane (conventionally about 7-50%). [0138] TLC: Eluent: AcOEt-MeOH 9/1; [0139] Developer: phosphomolybdic acid; [0140] Rf=0.3. [0141] 1H NMR (300 MHz; CDCl3): [0142] δ (ppm): 3.60 (t, 2H, J=6.1 Hz, -CH2NCS); 2.73 (m, 2H, -S(O)-CH2-); 2.50 (s, 3H, CH3); 1.82-2.00 (broad m, 4H, -CH2-CH2-). [0143] 13C NMR (75 MHz; CDCl3): [0144] δ (ppm): 53.48 (-CH2-NCS); 44.62 (-S(O)-CH2); 38.71 (CH3-S(O)-); 28.97 (-CH2-CH2-NCS); 20.067 (-S(O)-CH2-CH2-). [0145] UV spectrum: [0146] λmax=242 nm. [0147] Refractive index: nD20=1.3516
  • 26
  • [ 64-17-5 ]
  • [ 4478-93-7 ]
  • [ 1356472-67-7 ]
YieldReaction ConditionsOperation in experiment
84% Reflux; Inert atmosphere; 14 EXAMPLE 14 Synthesis of the Coupling Product of Sulforaphane with Ethanol EXAMPLE 14 Synthesis of the Coupling Product of Sulforaphane with Ethanol [0241] The sulforaphane obtained in Example 4 is solubilized in absolute ethanol. After degassing and setting it under nitrogen, the mixture is refluxed until total conversion. The ethanol is finally removed in the rotary evaporator. A viscous yellow liquid is obtained, it is purified on a chromatographic column in order to provide a beige solid with a yield of 84%. [0242] 1H NMR (300 MHz; CDCl3): [0243] Like for sulforamate, the presence of a minority tautomer is detected (66° A)/33%). O-ethyl 4-(methylsulfinyl)butylcarbamothioate [0244] δ (ppm): 6.65 (broad peak, 1H, -NH-); 4.45 (q, J=7.1 Hz, 2H, -O-CH2-CH3); 3.60 (q, J=6.6 Hz, 2H, CH2-NH-C(S)-); 2.75 (m, 2H, -CH2-S(O)-); 2.57 (s, 3H, -CH3-S(O)-); 1.86-1.79 (m, 4H, -CH2-CH2-); 1.29 (t, J=7.1 Hz, 3H, CH3-CH2-O-) [0245] Minority Tautomer: [0246] δ (ppm): 7.10 (broad peak, 1H, -NH-); 4.53 (q, J=7.1 Hz, 2H, -O-CH2-CH3); 3.31 (q, J=6.5 Hz, 2H, CH2-NH-C(S)-); 2.72 (m, 2H, -CH2-S(O)-); 2.57 (s, 3H, -CH3-S(O)-); 1.80-1.70 (m, 4H, -CH2-CH2-); 1.35 (t, J=7.1 Hz, 3H, CH3-CH2-O-) [0247] 13C NMR (75 MHz; CDCl3): [0248] δ (ppm): 190.57; 66.22; 53.66; 44.15; 38.55; 28.22; 19.82; 14.20 [0249] UV spectrum: [0250] λmax=242 nm [0251] Melting point: 58° C.
  • 27
  • [ 110-89-4 ]
  • [ 4478-93-7 ]
  • [ 1350914-98-5 ]
YieldReaction ConditionsOperation in experiment
In dichloromethane for 1h; Reflux; 10 EXAMPLE 10 Synthesis of N-(4-(methylsulfinyl)butyl)-piperidine-1-carbothioamide EXAMPLE 10 Synthesis of N-(4-(methylsulfinyl)butyl)-piperidine-1-carbothioamide N-(4-methylsulfinyl)butyl)piperidine-1-carbothioamide was synthesized by refluxing with heating for 1 hour in dichloromethane, 1.1 equivalents of piperidine in the presence of 1 equivalent of sulforaphane obtained in Example 4. At the end of the reaction, the solvent is evaporated. The thiourea was then crystallized as a yellowish solid and the amine excess is removed in the wash waters of the solid. The yield is 90% for the final step for coupling the amine on the sulforaphane. 1H NMR (300 MHz; CDCl3): δ (ppm): 6.16 (broad peak, 1H, -NH-); 3.75 (t, J=5.3 Hz, 4H, -CH2-N-CH2; piperidine); 3.70 (m, 2H, -CH2-NH-C(S)-); 2.73 (t, J=7.4 Hz, 2H, -CH2-S(O)-); 2.54 (s, 3H, CH3-S(O)-); 1.75-1.88 (m, 4H, -CH2-CH2-); 1.67-1.51 (m, 6H, -CH2-CH2-CH2-piperidine). 13C NMR (75 MHz; CDCl3): δ (ppm): 180.94; 53.36; 48.74; 44.94; 38.55; 28.00; 25.39; 24.20; 19.73. [0213] UV spectrum: [0214] λmax=218 and 242 nm [0215] Melting point: 92° C.
  • 28
  • [ 110-91-8 ]
  • [ 4478-93-7 ]
  • [ 1356346-82-1 ]
YieldReaction ConditionsOperation in experiment
95% In dichloromethane for 1h; Reflux; 12 Synthesis of N-(4-(methylsulfinyl)butyl)-morpholine-4-carbothioamide EXAMPLE 12 Synthesis of N-(4-(methylsulfinyl)butyl)-morpholine-4-carbothioamide N-(4-(methylsulfinyl)butyl)morpholine-4-carbothioamide was synthesized by refluxing with heating for 1 hour in dichloromethane, 1.1 equivalents of morpholine in the presence of 1 equivalent of sulforaphane obtained in Example 4. At the end of the reaction, the solvent is evaporated. The thiourea was then crystallized as a white solid and the amine excess is removed in the wash waters from the solid. The yield is 95% for the final step for coupling the amine on the sulforaphane. 1H NMR (300 MHz; CDCl3): δ (ppm): 6.46 (broad peak, 1H, -NH-); 3.83-3.69 (m, 10H, -CH2-N-CH2- ring +-CH2-O-CH2- ring +-CH2-NH-); 2.76 (t, J=7.0 Hz, 2H, -CH2-S(O)-); 2.57 (s, 3H, CH3-S(O)-); 1.96-1.81 (m, 4H, -CH2-CH2-). 13C NMR (75 MHz; CDCl3):[0229] δ (ppm): 182.43; 66.22; 52.84; 47.55; 44.97; 38.61; 27.49; 19.76. [0230] UV spectrum: [0231] λmax=218 and 242 nm [0232] Melting point: 101° C.
  • 29
  • (R,S)<SUB>S</SUB>-glucoraphanin [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
With myrosinase In aq. phosphate buffer Enzymatic reaction; 2.4 Enzyme bio-activation of RS-GRA and animal treatment RS-GRA (10mg/kg) was dissolved in PBS solution pH 7.2 and mouse treatment required the enzyme bioactivation of the phytochemical. The in situ action of the Myr enzyme (5μl/mouse) for 15min allowed us to have a bioactive RS-GRA quickly (Italian Patent pending MI2012A001774), before the ip treatment (Fig. 1).
  • 30
  • [ 4478-93-7 ]
  • [ 5188-07-8 ]
  • Sulforamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: sodium thiomethoxide With hydrogenchloride In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: D,L-sulforaphane In N,N-dimethyl-formamide at 20℃; 23 EXAMPLE 23 Synthesis of (4-methylsulfinyl-1-(S-methyl-dithio-carbamyl)-butane sulforamate EXAMPLE 23 Synthesis of (4-methylsulfinyl-1-(S-methyl-dithio-carbamyl)-butane sulforamate 5 equivalents of sodium methanethiolate are solubilized in DMF. The mixture is cooled to 0° C. and 5 equivalents of 37% HCl are added. The mixture is maintained for 1 hour at this temperature, and then 1 equivalent of sulforaphane obtained according to Example 4 is added. The medium is maintained with stirring, then the temperature is left to rise up to room temperature. At the end of the reaction, after extraction with dichloromethane and washing with the acid, the organic phases are collected, dried and the solvent is evaporated. The obtained product is then crystallized from ethyl acetate. The pure product is obtained as a whitish solid and has the following formula: [0347] TLC: [0348] Eluent: EtQAc/MeOH 40/2; Developer: phosphomolybdic acid; Rf=0.3 [0349] 1H NMR (300 MHz; CDCl3): [0350] Sulforamate: [0351] δ (ppm): 8.26 (a large, 1H, -CH2-NH-C(S)-); 3.77 (m, 2H, -CH2-NH-); 2.75 (m, 2H, -S(O)-CH2-); 2.59 (s, 6H, CH3-S(O)- and -S-CH3); 1.85 (m, 4H, -CH2CH2-) [0352] Tautomer (minority): [0353] 8.40 (broad s, 1H, -SH); 3.48 (m, 2H, -CH2-NH-); 2.76 (m, 2H, -S(O)-CH2); 2.64 (s, 6H, CH3S(O)- and -S-CH3); 2.59 1.85 (m, 4H, -CH2-CH2-) [0354] 13C NMR (75 MHz; CDCl3): [0355] Sulforamate: [0356] δ (ppm): 199.03; 5336; 46.26; 38.49; 27.13; 20.16; 18.00 [0357] Melting point: 96° C. [0358] UV Spectrum: λmax=250 and 272 nm
  • 31
  • [ 109-01-3 ]
  • [ 4478-93-7 ]
  • [ 75-09-2 ]
  • [ 1356472-66-6 ]
YieldReaction ConditionsOperation in experiment
97% In dichloromethane for 1h; Reflux; 11 Synthesis of 4-methyl-N-(4-(methylsulfinyl)-butyl)piperazine-1-carbothioamide EXAMPLE 11 Synthesis of 4-methyl-N-(4-(methylsulfinyl)-butyl)piperazine-1-carbothioamide 4-methyl-N-(4-(methylsulfinyl)butyl)piperazine-1-carbothioamide was synthesized by refluxing with heating for 1 hour in dichloromethane, 1.1 equivalents of piperazine in the presence of 1 equivalent of sulforaphane obtained in Example 4. At the end of the reaction, the solvent is evaporated. The thiourea was then recovered as a viscous oil on a silica gel chromatographic column and the yield is 97% for the final step for coupling the amine on the sulforaphane, 4-methyl-N-(4-(methylsulfinyl)butyl)piperazine-1-carbothioamide has the following formula: 1H NMR (300 MHz; CDCl3): δ (ppm): 6.24 (broad peak, 1H, -NH-); 3.84 (t, J=4.9 Hz, 4H, -CH2-N-CH2-ring); 3.74 (m, 2H, -CH2-NH-C(S)-); 2.75 (1, J=7.0 Hz, 2H, -CH2S(O)-); 2.57 (s, 3H, CH3-S(O)-); 2.43 (t, J=5.1 Hz, 4H, -CH2-N(Me)-CH2-ring); 2.30 (s, 3H, CH3-N ring); 1.93-1.83 (m, 4H, -CH2-CH2-). 13C NMR (75 MHz; CDCl3):0221] δ (ppm): 181.91; 54.45; 52.99; 47.30; 45.79; 45.03; 38.61; 27.67; 19.79. [0222] UV spectrum: [0223] λmax=217 and 242 nm [0224] Crystallization/recrystallization of 4-methyl-N-(4-(methylsulfinyl)-butyl)-piperazine-1-carbothioamide from ethyl acetate is advantageous and allows the compound to be obtained as a solid in which the melting point is 72° C.
  • 32
  • [ 50541-93-0 ]
  • [ 4478-93-7 ]
  • [ 1356346-85-4 ]
YieldReaction ConditionsOperation in experiment
93% In dichloromethane for 1h; Reflux; 13 Synthesis of 1-(1-benzyl-piperidin-4-yl)-3-4-(methylsulfinyl)butyl thiourea EXAMPLE 13 Synthesis of 1-(1-benzyl-piperidin-4-yl)-3-4-(methylsulfinyl)butyl thiourea 1-(1-benzylpiperidin-4-yl)-3-4-(methylsulfinyl)butyl thiourea was synthesized by refluxing with heating for 1 hour in dichloromethane, 1.1 equivalents of benzylpiperidine in the presence of 1 equivalent of sulforaphane obtained in Example 4. At the end of the reaction, the solvent is evaporated. The thiourea was then recovered as a very viscous oil which solidifies in the refrigerator on a silica gel chromatographic column and the yield is 93% for the final step for coupling the amine on the sulforaphane. 1H NMR (300 MHz; CDCl3): δ (ppm): 6.65 (broad peak, 1H, -NH-); 6.34 (broad peak, 1H, -NH-); 4.06 (broad peak, 1H, -NH-CH-); 3.56 (broad bulk, 2H, -CH2-NH-); 3.48 (s, 2H, -CH2-ph); 2.71-2.82 (m, 4H, -CH2-S(O)- piperidine ring); 2.58 (s, 3H, CH3-S(O)-); 2.18-1.42 (bulk of 4 multiplets, 10H, -CH2-CH2- piperidine ring). 13C NMR (75 MHz; CDCl3):[0237] δ (ppm): 181.33; 138.16; 129.07; 128.15; 126.97; 63.00; 53.48; 52.11; 51.04; 43.41; 38.55; 32.04; 28.00; 20.13. [0238] UV spectrum: [0239] λmax=243 nm [0240] Melting point: 120° C.
  • 33
  • 1-[5-(methylsulfinyl)-N-(sulfonatooxy)pentanimidoyl]-1-thio-β-D-glucopyranose [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
120.16 μmol With ascorbic acid at 38℃; for 0.5h; Enzymatic reaction; 4 Example 4 [00081] Equimolar Conversion of Glucoraphanin to Sulforaphane. A two-part experiment was conducted to further elucidate the role of ascorbic acid in modulating myrosinase activity. All solutions were prepared in 20 mM Tris-buffered saline, at pH 7.5, previously identified as an optimal for myrosinase activity; each sample tube had 100 mg of freeze-dried broccoli powder accurately weighed in as a source of myrosinase. Experiment was conducted at 38 °C for 2 hours, with sample aliquots removed in 30-minute increments, and both glucoraphanin and sulforaphane content assessed by HPLC. A strongly acidic "stop" solution was utilized to instantaneously inhibit further myrosinase activity in the removed aliquots. A control sample contained no ascorbic acid, and the enzymatic conversion proceeded unassisted by a co-factor. [00083] PART 1 . In the presence of the fixed concentration of ascorbic acid, 1 mmol/Liter, an increasing amount of broccoli seed extract (about 12% glucoraphanin, w/w) was added, ranging from 250 mg to 500 mg. [00084] PART 2. While keeping the amount of broccoli seed extract fixed at 250 mg, the concentration of ascorbic acid was varied from 0.4 mmol/Liter to 3.8 mmol/Liter. [00085] The table below presents glucoraphanin and sulforaphane expressed in pinoles. It is apparent that within the first 30 minutes in almost all the reaction mixtures, conversion of glucoraphanin to sulforaphane was complete. However, careful examination of the enzymatic conversion occurring in the control sample, without the stimulating effects of ascorbic acid, reveals an equimolar conversion of glucoraphanin to sulforaphane, i.e., the amount of glucoraphanin consumed results in the equivalent amount of sulforaphane produced. Glucoraphanin, moles Sulforaphane, moles Time, min 0 30 60 90 120 0 30 60 90 120 GR 250 mg AA O.O mM 58.02 48.57 37.52 26.58 15.67 3.42 12.08 22.27 33.17 42.89 GR 250 mg AA 1.0 mM 40.07 21.51 61.95 60.20 60.04 58.25 GR 300 mg AA 1.0 mM 49.31 24.18 74.40 73.04 72.19 70.56 GR 350 mg AA 1.0 mM 61.41 25.00 84.92 84.02 83.19 80.02 GR 400 mg AA 1.0 mM 71.35 1.56 26.71 96.60 95.38 93.39 91.16 GR 500 mg AA 1.0 mM 89.41 1.01 33.52 120.16 118.45 116.45 1 12.34 GR 250 mg AA O.4 mM 45.66 15.98 62.06 61.01 60.88 58.90 GR 250 mg AA 1.0 mM 35.24 26.49 62.19 60.62 60.41 59.10 GR 250 mg AA 2.0 mM 24.94 36.05 60.85 59.78 59.65 58.08 GR 250 mg AA 2.9 mM 22.24 38.20 59.95 59.34 58.77 56.99 GR 250 mg AA 3.8 mM 21.70 37.87 58.77 57.79 58.41 56.17 [00086] In the Part 2 of the experiment, the modulatory effect of the increasing concentration of ascorbic acid on the activity of myrosinase was assessed. An initial, apparently linear, increase in myrosinase-promoted conversion of glucoraphanin to sulforaphane is observed to about 2 mmol/L of ascorbic acid concentration, followed subsequently by a considerable leveling off. [00087] Finally, examination of sulforaphane yield of after 30 minutes within the PART 1 of the experiment, reveals that in the presence of 1 mmol/Liter of ascorbic acid, the fixed amount of myrosinase contained in 100 mg of freeze-dried broccoli sprout powder is capable of generating at least 200 pinoles of sulforaphane, in a predictably linear fashion. FIG. 1 , 2, 3, and 4 demonstrate the results of this study.
  • 34
  • [ 4478-93-7 ]
  • [ 10016-20-3 ]
  • [ 1498229-87-0 ]
YieldReaction ConditionsOperation in experiment
78.5% Stage #1: alpha cyclodextrin In water at 55℃; Inert atmosphere; Cooling with ice; Stage #2: D,L-sulforaphane In water at 20℃; for 16h; 2 a-Cyclodextrin (Wacker CAVAMAX W6 Food Grade, 3015g, 3.1 moles, 1 equivalent) was dissolved in distilled water (8L) by heating up to 55°C under nitrogen atmosphere. Thehomogeneous solution was cooled down to - 25°C using an ice-water bath and then degassed for-20 min by purging nitrogen. After degassing, it turned into a foggy solution. Aqueous solutionof sulforaphane was removed from the refrigerator (see previous step) and then added to theabove foggy a-cyclodextrin solution at once. At this stage reaction temperature was -18°C, and continued stirring at room temperature overnight ( -16h). The heterogeneous reaction mixturewas cooled down to 1-2 °C using ice-methanol bath and stirred for 3 hr at that temperature. Theprecipitated white solid was filtered and dried overnight under high vacuum at room temperatureby covering the filter funnel with a latex sheet. The white filter cake was transferred into a 10-Lrotovap flask and dried further at room temperature under a high vacuum to afford 2,802g of complex (98.7% pure by HPLC, 78.5% yield). All three batches were conducted at almost same scale and the reactions proceeded in similar way in terms of reaction time, yield, product purity and percentage loading ofsulforaphane on a-cyclodextrin 1HNMR (D20, 400 MHz); 81.99 (br, 4H), 2.73 (s, 3H), 2.98 (br, 2H), 3.60 (m, 12H), 3.70(br, 2H), 3.92(m, 24H), 5.11 (d, 6H). 13 CNMR (D20, 100 MHz); u~ 130.05, 101.82, 81.40, 74.05, 71.98, 71.84, 60.34, 52.02,44.94, 37.03, 29.29, 20.08..11 (d, 6H).
76.9% With dihydrogen peroxide In water at 0 - 55℃; Large scale; 1; 1A; 4 Example 1A: Formation of a complex of sulforaphane and α-cyclodextrin according to procedures in WO 2013/179057 To degassed a-cydodextrin (30 g, 0.01 eqv) in water (1 L) at room temperature was added 1-isothiocyanato-4-methylthiobutane (501 g, 1 eqv). The solution was cooled to 0°C and degassed for 30 mins. To the suspension was added 35% aqueous H2O2 (305 mi, 1 eqv) slowly while maintaining the internal temp below 4°C during the addition. The reaction mixture was stirred for 8 hr at ice bath temperature and was then allowed to warm to room temperature while stirring overnight. The solution was filtered to remove solids. The filtrate was refrigerated for 5 hr prior to use in the next step. α-cyclodextrin (3015 g, 1 eqv) was dissolved in water (8 L) by heating up to 55 °C, The solution was cooled down to room temperature and the sulforaphane filtrate from the previous step was added at once. The mixture was stirred at room temperature overnight. The reaction mixture was then cooled in an ice bath and stirred at that temperature for 3 hr. The precipitated solid was filtered through Buchner funnel and dried on the filter under vacuum overnight. The filter cake was transferred to a 10 L round-bottomed flask and dried under high vacuum at room temperature over the weekend to yield a white soiid (2.74 kg, 76.9% yieid; batch ref. 191PAL79). The soiid had a water content of 11.3% w/w by Karl-Fischer analysis and a purity by HPLC of 98.5%. 1-NMR analysis confirmed that Example 1A was a 1:1 sulforaphane:α-cyclodextrin complex.
YieldReaction ConditionsOperation in experiment
With tau class glutathione transferase GSTU16 In ethanol; acetonitrile at 30℃; for 0.0166667h; Enzymatic reaction;
  • 36
  • S-methyltetrahydrothiophenium fluoroborate [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: sodium azide / N,N-dimethyl-formamide / 16 h / 60 °C / Green chemistry 2.1: triphenylphosphine / diethyl ether / 3 h / 20 °C / Green chemistry 2.2: 1 h / 20 °C / Green chemistry 3.1: dihydrogen peroxide; acetic acid / 1 h / 20 °C / Green chemistry
Multi-step reaction with 3 steps 1.1: sodium azide / N,N-dimethyl-formamide / 16 h / 60 °C 2.1: triphenylphosphine / diethyl ether / 3 h / 20 °C 2.2: 1 h / 20 °C 3.1: dihydrogen peroxide; acetic acid / 1 h / 20 °C
  • 37
  • [ 57775-01-6 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: triphenylphosphine / diethyl ether / 3 h / 20 °C / Green chemistry 1.2: 1 h / 20 °C / Green chemistry 2.1: dihydrogen peroxide; acetic acid / 1 h / 20 °C / Green chemistry
  • 38
  • [ 4478-93-7 ]
  • [ 3386-97-8 ]
YieldReaction ConditionsOperation in experiment
80 %Chromat. In water at 120℃; the injection of sulforaphane (I) in gas chromatography shows that 80% of the product is degraded into 3-butenylisothiocyanate (4) according to the reaction (I).It has been demonstrated that this product specifically stems from thermal degradation of sulforaphane in the ther(1) mostated injector at 250° C. of gas phase chromatography (see FIG. 1, A). Indeed, when the sample is directly injected onto the column without passing through the injector, nodegradation peak is observed (see FIG. 1, B).
  • 39
  • [ 4478-93-7 ]
  • C12H24N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: chiral column (Chiralpak AD-RH) / acetonitrile / 35 °C / Resolution of racemate 2: triethylamine / ethanol; i-Amyl alcohol / 1 h / 40 °C
  • 40
  • [ 4478-93-7 ]
  • [ 142825-10-3 ]
  • [ 155320-20-0 ]
YieldReaction ConditionsOperation in experiment
With chiral column (Chiralpak AD-RH) In acetonitrile at 35℃; Resolution of racemate;
  • 41
  • [ 4478-93-7 ]
  • [ 63-91-2 ]
  • C15H22N2O3S2 [ No CAS ]
  • C15H22N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 42
  • [ 4478-93-7 ]
  • [ 73-22-3 ]
  • C17H23N3O3S2 [ No CAS ]
  • C17H23N3O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 43
  • [ 56-41-7 ]
  • [ 4478-93-7 ]
  • C9H18N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 44
  • [ 72-18-4 ]
  • [ 4478-93-7 ]
  • C11H22N2O3S2 [ No CAS ]
  • C11H22N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 45
  • [ 61-90-5 ]
  • [ 4478-93-7 ]
  • C12H24N2O3S2 [ No CAS ]
  • C12H24N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 46
  • [ 63-68-3 ]
  • [ 4478-93-7 ]
  • C11H22N2O3S3 [ No CAS ]
  • C11H22N2O3S3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In ethanol; i-Amyl alcohol at 40℃; for 1h;
  • 47
  • [ 4478-93-7 ]
  • [ 13242-44-9 ]
  • 2-(dimethylamino)ethyl[4-(methylsulfinyl)butyl]dithiocarbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
11.9% With sodium hydroxide In water at 40℃; for 12h; Inert atmosphere; The synthesis of 2- (dimethylamino) ethyl [4- (methylsulfinyl) butyl] dithiocarbamate (Compound 2) is as follows: In a 25 mL two-necked round bottom flask,Add compound2-dimethylaminothioethanol hydrochloride (240 mg, 1.69 mmol) and 10 mL of a 95% ethanol solution,Followed by the addition of the compound1-isothiocyanato-4-methanesulfonylbutane 330 mg (1.86 mmol)The reaction solution was adjusted to a pH of about 6 with 1 M sodium hydroxide aqueous solution,The reaction solution was heated to 40 ° C under argon atmosphere and stirred for 12 hours by TLC(Dichloromethane: methanol = 10: 1,0.5% aqueous ammonia) to detect the reaction,Found that the reaction is not complete,With the increase in time will appear more side effects products.To the reaction solution was added 1 M aqueous sodium hydroxide solution to adjust the pH to alkaline,The reaction solution was spin-dried,The resulting residual material was dissolved in dichloromethane,Washed twice with saturated sodium carbonate solution and saturated brine,The resulting organic phase was dried over anhydrous sodium sulfate and concentrated,To give a crude product as a pale yellow oil,Purification by silica gel column (dichloromethane: methanol = 150: 1)The product is oily viscous liquid,Weight of 56.9mg,The yield was 11.9%.
  • 48
  • [ 4478-93-7 ]
  • C8H17NO2S [ No CAS ]
  • C14H28N2O3S3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88.7% With dmap In dichloromethane at 20℃; for 10h; Inert atmosphere; The synthesis of 2- (dimethylamino) ethyl-3-mercapto-2-methylpropyl- (4- (methylsulfinyl) butyl) dithiocarbamate (Compound 4) In a 10 mL two-bottle,1-isothiocyanato-4-methanesulfonylbutane60.3 mg (0.34 mmol) was dissolved in 5 mL of dichloromethane,19.5 mg (0.11 mmol) of N, N-dimethylaminopyridine was added2- (dimethylamino) ethyl-3-mercapto-2-methylpropyl ester 47 mg, (0.25 mmol)The system was stirred under argon at room temperature for 10 h,The reaction was carried out by TLC (dichloromethane: methanol = 20: 1, 0.5% NH3 · H2O). After completion of the reaction, the solvent was reINmoved by rotary evaporator to give the crude product,Purification by silica gel column chromatography (dichloromethane: methanol = 50: 1) gave a yellow viscous solid,Weight of 105mg,The yield was 88.7%.
  • 49
  • [ 4478-93-7 ]
  • C8H19NO2S [ No CAS ]
  • C14H30N2O3S3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
64.5% With triethylamine In dichloromethane at 20℃; for 10h; Inert atmosphere; Synthesis of 2- (2- (2- (dimethylamino) ethoxy) ethoxy) ethylthio- (4- (methylsulfinyl) butyl) dithiocarbamate (Compound 6) The process is as follows: In a 25 mL two-bottle,1-isothiocyanato-4-methanesulfonylbutane280 mg (1.58 mmol) was dissolved in 15 mL of dichloromethane,A solution of triethylamine (26.6 mg, 0.26 mmol) was added2- (2- (2- (dimethylamino) ethoxy) ethoxy) ethanethiol (254.4 mg, 1.32 mmol)The system was stirred under argon at room temperature for 10 h,The reaction was carried out by TLC (dichloromethane: methanol = 20: 1,0.5% NH3 · H2O)After the reaction is complete,The solvent was removed by rotary evaporator,Get the crude,Purification by silica gel column chromatography (dichloromethane: methanol = 50: 1) gave a yellow viscous solid,Weight of 250mgThe yield was 64.5%.
64.5% With triethylamine In dichloromethane at 20℃; for 10h; Inert atmosphere; General procedure for the synthesis of compound 8 General procedure: A solution of compound 7 (15.8 mmol) in DCM (150 mL), Et3N (266 mg, 2.60 mmol) and compound 6 (2.5 g, 13.2 mmol) was stirred at room-temperature for about 10 h with Ar protection. The reaction mixture was evaporated under reduced pressure and the crude material was purified by column chromatography (DCM : MeOH = 50:1) to obtain compound 8.. Compound 8a: yellow oil, yield 64.5%. 1H-NMR (400 MHz, CDCl3) δ 8.66 (s, 1H), 3.75 (t, J = 5.8 Hz, 4H), 3.69-3.58 (m, 6H), 3.37 (t, J = 5.7 Hz, 2H), 2.79-2.71 (m, 2H), 2.64 (t, J = 5.7 Hz, 2H), 2.58 (s, 3H), 2.35 (s, 6H), 1.87 (br, 4H). 13C-NMR (100 MHz, CDCl3) δ 197.4, 70.5, 70.4, 68.8, 58.6, 53.7, 46.4, 45.6, 38.7, 35.2, 27.2, 20.2.
  • 50
  • [ 20582-85-8 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1.1: triethylamine / dichloromethane / 1 h / -10 - 20 °C 2.1: sodium azide; tetrabutylammomium bromide / acetone; water / 6 h / Reflux; Inert atmosphere 3.1: triphenylphosphine / toluene / 4 h / 0 - 20 °C / Inert atmosphere 3.2: 24 h / 20 °C 4.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 3 h / -5 °C
  • 51
  • 4-methylthio-1-butyl methanesulfonate [ No CAS ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: sodium azide; tetrabutylammomium bromide / acetone; water / 6 h / Reflux; Inert atmosphere 2.1: triphenylphosphine / toluene / 4 h / 0 - 20 °C / Inert atmosphere 2.2: 24 h / 20 °C 3.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 3 h / -5 °C
YieldReaction ConditionsOperation in experiment
In aq. phosphate buffer at 100℃;
  • 53
  • [ 4478-93-7 ]
  • [ 70-18-8 ]
  • (11R,16S)-16-amino-11-((carboxymethyl)carbamoyl)-13-oxo-8-methylsulfinyl-2,9-dithia-7,12-diazaheptadecan-17-oic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With sodium hydroxide; In ethanol; water; at 23℃; for 1h;pH 7 - 8; To a solution of N5-((R)-1-((carboxymethyl)amino)-3-mercapto-1-oxopropan-2-yl)-L-glutamine(100 mg, 0.325 mmol) in a mixture of Ethanol (2 mL) and Water (2.000 mL), was added 1M aqNaOH til pH = 7 - 8, then 1-isothiocyanato-4-(methylsulfinyl)butane (63.5 mg, 0.358 mmol) inethanol (2 mL) was added. The reaction mixture was stirred at 23 C for 1 hr, the solvent wasevaporated in vacuo and the crude product was purified on a Gilson HPLC (YMC C18 5 mm/12nm 50 x 20 mm preparatory column), eluting at 20 mL/min with a linear gradient running fromwater to acetonitrile to afford (11R,16S)-16-amino-11-((carboxymethyl)carbamoyl)-13-oxo-8-methylsulfinyl-2,9-dithia-7,12-diazaheptadecan-17-oic acid 26 (83 mg, 53%). 1H NMR(400 MHz CD3OD) delta 4.69 - 4.76 (m, 1 H), 3.90 (dd, J=14.31, 4.52 Hz, 1 H), 3.67 - 3.85 (m, 4H), 3.62 (t, J=5.77 Hz, 1 H), 3.53 (dd, J=14.18, 8.66 Hz, 1 H), 2.78 - 2.97 (m, 2H), 2.66 (s, 4 H),2.45 - 2.60 (m, 2 H), 2.15 (br. s., 2 H), 2.05 (s, 1 H), 1.76 - 1.93 (m, 5 H).
With sodium hydrogencarbonate; In aq. buffer; at 25℃; for 1h;pH 10; SFN-GSH was synthesized according to the following procedure (Pernice et al., 2009): 2.2 mumol of SFN and 4.5 mumol of GSH were dissolved in 500 muL of 0.5 M sodium hydrogen carbonate buffer pH 10 and stirred at 25 C for 1 h. The reaction was stopped by adjusting the pH to 5 using 36% hydrochloric acid. For SFN-Lys preparation 2.2 mumol of SFN and 5.4 mumol of lysine were dissolved in 500 muL of 0.5 M sodium hydrogen carbonate buffer pH 10 and stirred at 25 C for 1 h. Molecular weight and structures of the conjugates were confirmed by electrospray ionization MS and their retention time and mass spectra were utilized to identify the adduct in the samples.
  • 54
  • [ 4478-93-7 ]
  • None [ No CAS ]
  • None [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydrogencarbonate In ethanol; water
  • 55
  • [ 4478-93-7 ]
  • [ 75-08-1 ]
  • ethyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87.5% With sodium hydrogencarbonate In ethanol; water at 20℃; for 5h; 2 Preparation of W101: Weigh the raw material NaHCO3 0.26g (3.2mmol) in a 100ml single-necked flask, add 10ml of water to dissolve, magnetically stir, then add ethanethiol 0.19g (3mmol) to it, finally weighed 0.53g (3mmol) of lysin diluted with 20ml of ethanol The solution was dissolved and added to the reaction solution, and reacted at room temperature for 5 hours. The reaction was followed by a thin layer chromatography plate. The developing solvent was ethyl acetate:methanol = 5:1. After completion of the reaction, the organic solvent ethanol was evaporated, and then diluted with 20 ml of water, and then, ethyl acetate (60 ml), and the mixture was extracted three times with 20 ml each time. The extract was dried over anhydrous MgSO4 and filtered, and the filtrate was evaporated. The final product was obtained in an amount of 0.63 g, yield: 87.5%.
87.5% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 1 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.4.1.2.1 Ethyl (4-(methylsulfinyl)butyl)carbamodithioate (2a) Yellow oil; Yield 87.5%; HPLC Rt = 21.36min; 1H NMR (400 MHz, DMSO-d6): δ = 3.67 (m, 2H), 3.15 (m, 2H), 2.71 (m, 2H), 2.52 (s, 3H), 1.67 (m, 4H), 1.22(t, j = 7.27, 2H). 13C NMR (100 MHz, DMSO-d6): δ = 14.5, 19.5, 26.7, 27.9, 37.9, 46.0, 52.9, 196.0. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C8H18NOS3 240.0551; Found 240.0544.
  • 56
  • [ 4478-93-7 ]
  • [ 75-33-2 ]
  • isopropyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
44.7% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 2 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 57
  • [ 513-53-1 ]
  • [ 4478-93-7 ]
  • sec-butyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 3 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 58
  • [ 4478-93-7 ]
  • [ 541-31-1 ]
  • 3-methylbutyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
19.4% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 4 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 59
  • 2-methyl-1-butanethiol [ No CAS ]
  • [ 4478-93-7 ]
  • 2-methylbutyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 5 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 60
  • [ 4478-93-7 ]
  • [ 1190-73-4 ]
  • 2-acetamidoethyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
31.5% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 6 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 61
  • [ 4478-93-7 ]
  • [ 17042-24-9 ]
  • 3-oxopentan-2-yl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
63.6% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 7 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 62
  • [ 4478-93-7 ]
  • [ 2935-90-2 ]
  • methyl 3-(((4-(methylsulfinyl)butyl)carbamothioyl)thio)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70.8% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 8 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 63
  • [ 4478-93-7 ]
  • [ 100-53-8 ]
  • benzyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
62.2% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 9 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 64
  • [ 4478-93-7 ]
  • [ 4498-99-1 ]
  • 4-methylbenzyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
72.3% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 10 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 65
  • [ 4478-93-7 ]
  • [ 6258-60-2 ]
  • 4-methoxybenzyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
91.9% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 11 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 66
  • [ 4478-93-7 ]
  • [ 6258-66-8 ]
  • p-chlorobenzyl N-[4-(methylsulfinyl)butyl]carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
91.8% With sodium hydrogencarbonate; In ethanol; water; at 20℃;Inert atmosphere; General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 67
  • [ 4478-93-7 ]
  • [ 106-45-6 ]
  • p-tolyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83.3% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 13 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 68
  • [ 4478-93-7 ]
  • [ 4946-13-8 ]
  • 4-ethylphenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 14 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 69
  • [ 4478-93-7 ]
  • [ 2396-68-1 ]
  • 4-(tert-butyl)phenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
72.8% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 15 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 70
  • [ 696-63-9 ]
  • [ 4478-93-7 ]
  • 4-methoxyphenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
63.2% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 16 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 71
  • [ 371-42-6 ]
  • [ 4478-93-7 ]
  • 4-fluorophenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
16.3% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 17 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 72
  • [ 4478-93-7 ]
  • [ 106-54-7 ]
  • 4-chlorophenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
10% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 18 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 73
  • [ 4478-93-7 ]
  • [ 106-53-6 ]
  • 4-bromophenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
26.7% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 19 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 74
  • [ 4478-93-7 ]
  • [ 1126-81-4 ]
  • 4-acetamidophenyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
53.4% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 20 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 75
  • [ 4410-99-5 ]
  • [ 4478-93-7 ]
  • phenethyl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81.1% With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; 21 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures.
  • 76
  • [ 1072-99-7 ]
  • [ 4478-93-7 ]
  • 1-methylpiperidin-4-yl (4-(methylsulfinyl)butyl)carbamodithioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
39% In tetrahydrofuran at 0 - 23℃; for 2h; 1-methylpiperidin-4-yl (4-(methylsulfinyl)butyl)carbamodithioate (22). (±)-Sulforaphane (490 mg, 2.77 mmol) was dissolved in tetrahydrofuran (THF) (8 mL) andchilled to 0 °C. To this solution was added 1-methyl-4-piperidinethiol (330 mg, 2.51 mmol) inTHF (1 mL). The reaction was allowed to warm up to 23 °C and stirred for 2 h. Solvent wasconcentrated and purified on a Gilson HPLC (YMC C18 5 μm/12 nm 50 x 20 mm preparatorycolumn), eluting at 20 mL/min with a linear gradient running from 5% CH3CN/H2O to 65%CH3CN/H2O over 10 min. to provide 1-methylpiperidin-4-yl (4-(methylsulfinyl)butyl)carbamodithioate (22) (299.2 mg, 39%).
  • 77
  • [ 4478-93-7 ]
  • [ 7149-10-2 ]
  • C14H22N2O3S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% Stage #1: vanillylamine hydrochloride With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 0.166667h; Inert atmosphere; Stage #2: D,L-sulforaphane In N,N-dimethyl-formamide at 20℃; for 10h; 2 The synthesis of compound 20a is as follows Take a dry 25 mL round bottom flask.The vanillinamine hydrochloride (100 mg, 0.53 mmol) was dissolved in 1 mL of re-distilled DMF, then DIPEA (68.20 mg, 0.53 mmol) was added with stirring.The reaction system was protected with argon gas and stirred at room temperature for 10 min to dissolve the material.Then, Compound 18 (93.48 mg, 0.53 mmol) dissolved in 1 mL of DMF was added to the reaction, and the reaction was stirred at normal temperature for 10 h. The reaction of the reaction raw materials was monitored by TLC.The reaction solution was quenched with water and extracted with dichloromethane (5 mL×3).The organic phase was collected and dried over anhydrous sodium sulfate, filtered, concentrated and purified on silica gel.The pale yellow viscous oily liquid product (190 mg, yield 98%) was obtained.
  • 78
  • [ 51-67-2 ]
  • [ 4478-93-7 ]
  • C14H22N2O2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
98.62% In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; 2 The synthesis of compound 20b is as follows Take a dry 25 mL round bottom flask.P-hydroxyphenylethylamine (50 mg, 0.36 mmol) was dissolved in 3 mL of re-distilled DMF.Compound 18 (64.62 mg, 0.36 mmol) was added to the reaction system.The reaction system was protected with argon gas, and the reaction was stirred at normal temperature for 10 hours.After TLC monitors the reaction of the reaction materials,The reaction solution was quenched with water and extracted with dichloromethane (3 mL×3).The organic phase was collected and dried over anhydrous sodium sulfate, filtered, concentrated and purified on silica gel.The pale yellow viscous oily liquid product (122 mg, yield 98.62%) was obtained.
  • 79
  • [ 2799-72-6 ]
  • [ 15590-23-5 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
64.7% In tetrahydrofuran at -30℃; for 3h; 4.3; 5.3; 6.3; 7.3; 8.3 Step 3: The specific synthesis method of synthesizing sulforaphane by 3-chloroisothiocyanopropane and methylsulfinyl sodium is as follows: The clear colorless sodium methylsulfonate liquid prepared in the first step is mixed with tetrahydrofuran and the temperature of the mixture is controlled at -30 ° C.The 3-chloroisothiocyanopropane prepared in the second step is added dropwise to the mixed solution at a molar ratio of 3-chloroisothiocyanopropane to sodium methylsulfonate of 1:2.After the completion of the dropwise addition, the original temperature was maintained for 3 hours to complete the reaction, and the mixture was filtered, distilled under reduced pressure, and fractions were collected.It is purified sulforaphane with a yield of 64.7% and a product purity of 98.7%.
YieldReaction ConditionsOperation in experiment
73% With dioxouranium(VI) acetate hydrate; phosphoric acid; oxygen In water; acetonitrile for 24h; Irradiation; 38 Synthesis of compound 2a General procedure: In a 25mL reaction tube, add uranyl acetate hydrate (1.7mg, 4 * 10-3mmol),4-methylphenyl (n-butyl) sulfide (36.0 mg, 0.2 mmol), water (36 mg, 2 mmol), phosphoric acid (12 μL, 0.2 mmol), acetonitrile (1 mL), evacuate for oxygen,Stir for 24 hours under three 2 watt LED lights,After the reaction is completed, it is dried, filtered, and concentrated.The colorless liquid 2a (37.2 mg, 95%) was separated by column chromatography (PE / EA = 2/1).
  • 81
  • [ 4478-93-7 ]
  • [ 19246-18-5 ]
  • sulforaphane cysteine-glycine [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With pyridine In ethanol for 5h; Darkness; 4.3. Chemical Synthesis of SFN-CG DL-SFN-CG was synthesized using a modification of the methods described by Kassahun et al. [38]and Hauder et al. [26]. In our modied method NaOH solution pH 8.0 was replaced with pyridine,a Lewis base. 7.24 mg of CysGly (4 eq, 0.04044 mmol) dissolved in 100 L of 50% EtOH and 1.8 mg ofSFN (1 eq, 0.01015 mmol) dissolved in 100 L of EtOH were mixed together in an Eppendorf tube.Three drops of pyridine were added using a syringe. Pyridine was used in excess and thus the exactamount was not measured. The reaction mixture was stirred for 5 h in the dark. Reaction progress wasmonitored qualitatively using LC-MS to check if levels of SFN changed. After 5 h the reaction wasstopped using 10 L 1M HCl. The reaction mixture was then diluted with MilliQ water to a volumeof 600 L. Two subsequent SPE clean-up steps were performed. C18 SPE cartridges were washedwith 6 mL 0.1% formic acid in acetonitrile and conditioned with 6 mL of 0.1% formic acid in water.The reaction mixture was loaded and washed with 2 mL 0.1% formic acid in water. The reactionproduct was eluted using 2 mL 10% acetonitrile 0.1% formic acid solution, collecting 0.5 mL fractions.Two subsequent SPE purifications were used to purify SFN-CG. The first SPE purification filtered outpyridine but did not remove excess of CysGly due to the ethanol content in the crude reaction mixture. After the rst SPE purication, fractions 1±5 were collected and concentrated under nitrogen streamat 20 C. After the second purification the pure product was obtained from fractions 2-5 after dryingunder vacuum.In total, 2.1 mg (58% yield) of white solid; HRAM ESI-MS(+): m/z 356.07617 (100; [M + H],C11H22O4N3S3, delta ppm 1.474); 1H NMR (600 MHz, DMSO-d6), δ 1.67 (m, 4 H, CH), 2.52 (s, 3 H,CH3), 2.66 and 2.77 (m, 2 H, CH), 3.34 (dd, 1 H, CH), 3.50 (dd, 1 H, CH), 3.60 (t, 3 H, CH2 and CH), 3.76(s, 2 H, CH2).)
  • 82
  • [ 4478-93-7 ]
  • 3-methyl-5H-1,4,2-dioxazol-5-one [ No CAS ]
  • C8H14N2O2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With carbonyl(5,10,15,20-tetraphenylporphyrinato)ruthenium(II) In toluene at 20℃; for 4h;
  • 83
  • [ 4478-93-7 ]
  • 3-(perfluorophenyl)-1,4,2-dioxazole-5-one [ No CAS ]
  • C13H11F5N2O2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With carbonyl(5,10,15,20-tetraphenylporphyrinato)ruthenium(II) In toluene at 20℃; for 4h;
  • 84
  • [ 163956-72-7 ]
  • [ 4478-93-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: hydrazine hydrate / ethanol / Reflux 2: sodium hydrogencarbonate / dichloromethane
  • 85
  • [ 4478-93-7 ]
  • [ 2949-92-0 ]
  • [ 3386-97-8 ]
  • (Z)-4-methylthio-3-butenyl isothiocyanate [ No CAS ]
  • (E)-4-methylthio-3-butenyl isothiocyanate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With water at 160℃; for 0.5h; Sealed tube;
  • 86
  • [ 4478-93-7 ]
  • [ 141-43-5 ]
  • N-(4-methylsulfinylbutyl)-N'-(2-hydroxyethyl)thiourea [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 60℃; for 2h;
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