Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH2:1]([NH2:3])[CH3:2].Cl[C:5]1[CH:14]=[C:13]2[C:8]([C:9](=[O:15])[NH:10][CH:11]=[N:12]2)=[CH:7][C:6]=1[N+:16]([O-:18])=[O:17].O>C(O)C>[CH2:1]([NH:3][C:5]1[CH:14]=[C:13]2[C:8]([C:9](=[O:15])[NH:10][CH:11]=[N:12]2)=[CH:7][C:6]=1[N+:16]([O-:18])=[O:17])[CH3:2]
Reactant: CCN
Reactant: O=c1[nH]cnc2cc(Cl)c([N+](=O)[O-])cc12
Solvent: O
Solvent: CCO
Product: CCNc1cc2nc[nH]c(=O)c2cc1[N+](=O)[O-]
Temperature: 110 °C
Reaction time: 4 h
Yield: 39 %

Procedure:
A 70% aqueous ethylamine solution (40 ml) was added to a solution (70 ml) of 7-chloro-6-nitro-4(3H)-quinazolone (6.31 g, 28.0 mmol) in ethanol and the mixture was heated with stirring at 110° C. for 4 hours in a sealed tube. After cooling to room temperature, the reaction mixture was poured into water and the precipitated crystals were collected by filtration. The crystals were washed with ethanol and dried to give the title compound (2.6 g, 39%).
Reaction SMILES: [CH3:1][Si:2]([CH3:15])([CH3:14])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[CH:11]=[C:10]([C:12]#[N:13])[N:9]=[CH:8]1.C1C(=O)N([Br:23])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl.CCOC(C)=O>[Br:23][C:8]1[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:15])([CH3:14])[CH3:1])[CH:11]=[C:10]([C:12]#[N:13])[N:9]=1
Reactant: C[Si](C)(C)CCOCn1cnc(C#N)c1
Reactant: O=C1CCC(=O)N1Br
Agent: CC(C)(C#N)N=NC(C)(C)C#N
Solvent: ClC(Cl)(Cl)Cl
Solvent: CCOC(C)=O
Product: C[Si](C)(C)CCOCn1cc(C#N)nc1Br
Temperature: 60 °C
Yield: 77.9 %

Procedure:
To a solution of 1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole-4-carbonitrile (0.70 g, 3.1 mmol) (as prepared in the previous step) in CCl4 (10 mL) was added NBS (0.61 g, 3.4 mmol) and AIBN (cat), and the mixture heated at 60° C. for 4 h. The reaction was diluted with EtOAc (30 mL) and washed with NaHCO3 (2×30 mL) and brine (30 mL) and the organic layer was dried over Na2SO4 and then concentrated. The title compound was eluted from a 20-g SPE cartridge (silica) with 30% EtOAc/hexane to give 0.73 g (77%) of a yellow solid. Mass spectrum (CI (CH4), m/z) Calcd. for C10H16BrN3OSi, 302.0/304.0 (M+H), found 302.1/304.1.
Reaction SMILES: [CH3:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[Br:13]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl.ClCCl>[Br:13][CH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]
Reactant: Cc1ccc(C#N)cc1[N+](=O)[O-]
Reactant: O=C1CCC(=O)N1Br
Agent: O=C(OOC(=O)c1ccccc1)c1ccccc1
Solvent: ClCCl
Solvent: ClC(Cl)(Cl)Cl
Product: N#Cc1ccc(CBr)c([N+](=O)[O-])c1
Yield: 44.9 %

Procedure:
A solution of 4-methyl-3-nitro-benzonitrile (3.0 g, 18.5 mmol), N-bromosuccinimide (4.12 g), and benzoyl peroxide (0.224 g) in carbon tetrachloride was refluxed overnight. The reaction mixture was diluted with dichloromethane and washed with sodium bicarbonate solution and brine, dried, and concentrated. The residue was purified by silica gel chromatography in 10% ethyl acetate hexanes to give compound 65a (2.0 g, 45%).
Reaction SMILES: Br[C:2]1[CH:3]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[N:6][CH:7]=1.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18].C(N(CC)CC)C>[Cu]I.C1COCC1>[CH3:16][Si:17]([C:20]#[C:21][C:2]1[CH:3]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[N:6][CH:7]=1)([CH3:19])[CH3:18]
Reactant: CC(C)(C)OC(=O)Nc1cncc(Br)c1
Reactant: C#C[Si](C)(C)C
Agent: [Cu]I
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CC(C)(C)OC(=O)Nc1cncc(C#C[Si](C)(C)C)c1
Temperature: 50 °C
Yield: 62.6 %

Procedure:
To a solution of tert-butyl (5-bromopyridin-3-yl)carbamate (3.00 g, 11.0 mmol) and THF (30 mL) was added (trimethylsilyl)acetylene (1.60 g, 16.3 mmol), (triphenylphosphine)palladium(II) chloride (0.31 g, 0.44 mmol), copper(I) iodide (84 mg, 0.44 mmol) and triethylamine (1.7 mL, 12 mmol) under nitrogen atmosphere. The mixture was heated at 50° C. overnight. The solvent removed in vacuo. The residue was diluted with EtOAc and water. The organic layer was separated, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude residue was purified by flash column chromatography to yield the desired product (2.0 g, 63%). LCMS calculated for C15H23N2O2Si(M+H)+: m/z=291.1.
Reaction SMILES: [NH2:1][C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[C:12]([N:19]1[CH2:26][CH2:25][CH2:24][C@H:20]1[C:21](O)=[O:22])([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13]>ClCCl>[C:15]([O:14][C:12]([N:19]1[CH2:26][CH2:25][CH2:24][C@H:20]1[C:21]([NH:1][C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6])=[O:22])=[O:13])([CH3:18])([CH3:17])[CH3:16]
Reactant: Cc1c(N)cccc1C(=O)O
Reactant: CC(C)(C)OC(=O)N1CCC[C@H]1C(=O)O
Solvent: ClCCl
Product: Cc1c(NC(=O)[C@@H]2CCCN2C(=O)OC(C)(C)C)cccc1C(=O)O
Reaction time: 18 h
Yield: 45 %

Procedure:
N-(3-Dimethylaminopropyl)-N-ethylcarbodimide HCl salt (3.1 g, 16.6 mmol) was added to a suspension of 3-amino-2-methylbenzoic acid (2.5 g, 16.6 mmol) and N-Boc-L-proline (3.5 g, 16.6 mmol) in dichloromethane (40 mL). The reaction mixture was stirred under nitrogen for 18 h, diluted with solvent (1 vol) and washed with 1N HCl, brine, and dried (MgSO4). Concentration gave a foam with was applied to a 40 M Biotage SiO2 column, and eluted by gradient 20%-60% B (1000 mL); A=1% acetic acid/hexanes; B=1% acetic acid/ethyl acetate to give J.36 (S)-3-(1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido)-2-methylbenzoic acid 2.6 g (45%). 1H NMR (300 MHz, DMSO-d6) δ: 12.5 (br. s, 1H), 9.52/9.46 (s, 1H), 7.57 (d, J=7.3 Hz, 1H), 7.44-7.40 (m, 1H), 7.29-7.24 (m, 1H), 4.32-4.28 (m, 1H), 3.47-3.48 (m, 1H), 3.34-3.29 (m, 1H), 2.33 (s, 3H), 1.93-1.80 (m, 4H), 1.41/1.36 (s, 9H). LC (Cond.-J1): 1.55 min; LCMS: Anal. Calcd. for [M+H]+ C18H25N2O5: 349.18; found 349.33.
Reaction SMILES: Cl.[NH2:2][OH:3].C(=O)(O)[O-].[Na+].[S:9]1[CH:13]=[CH:12][CH:11]=[C:10]1[C:14](=O)[C:15]([OH:17])=[O:16].C(O)C>O>[OH:3][N:2]=[C:14]([C:10]1[S:9][CH:13]=[CH:12][CH:11]=1)[C:15]([OH:17])=[O:16]
Reactant: NO
Reactant: O=C(O)C(=O)c1cccs1
Agent: Cl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: O
Solvent: CCO
Product: O=C(O)C(=NO)c1cccs1

Procedure:
A cooled solution of hydroxylamine hydrochloride (0.884 g) and sodium bicarbonate (1.08 g) in water (20 ml.) was added to a cooled (0° ) solution of thien-2-yl-glyoxylic acid (2.0 g) and sodium bicarbonate (1.08 g) in water (20 ml.). After two days at 20° the solution was extracted with ether, cooled and acidified with concentrated hydrochloric acid. The resulting white solid was filtered off (0.564 g) and the filtrate was then thoroughly extracted with ether. The combined extracts were washed with brine, dried and concentrated. The solid residue was triturated with benzene to give the exime (synisomer) (1.05 g; 51%), m.p. 132°, λmax. (ethanol) 284 nm (Ε9,500),νmax. (Nujol) 2590 and 1706 (SO2H) and 1655 cm-1 (C=N), τ (DMSO-d6), -2.5 to -0.5 (broad multiplet; N-OH and COOH), 2.36 (multiplet; thienyl C-5 H) and 2.82 (multiplet; thienyl C-3 H and C-4 H).
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.C(N(CC)CC)C.[C:18](Cl)(=[O:20])[CH3:19].C(=O)([O-])[O-].[K+].[K+]>ClCCl>[C:18]([NH:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1)(=[O:20])[CH3:19]
Reactant: Nc1ccc([N+](=O)[O-])cn1
Reactant: CC(=O)Cl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: CC(=O)Nc1ccc([N+](=O)[O-])cn1
Temperature: 25 °C
Reaction time: 1 h
Yield: 41 %

Procedure:
To a solution of 2-amino-5-nitropyridine (4.0 g, 28.8 mmol ) in dichloromethane (15 ml) were added 176 mg (31.6mmol) of 4-N,N'-dimethylaminopyridine (DMAP), 4.41 ml of triethylamine (31.6 mmol) and 2.16 ml (31.6 mmol) of acetyl chloride in turn, and the mixture was stirred at room temperature for 1 hour. A 1M aqueous solution of potassium carbonate was added to the mixed suspension to neutralize it. Extraction with chloroform was repeated three times, and the extract was dried over magnesium sulfate. The solvent was removed, and the residue was subjected to silica gel column chromatography (eluent: chloroform). Recrystallization from chloroform-hexane gave 2.14 g of the intended product as a flesh-colored powder (yield: 49%).
Reaction SMILES: [Mg].II.[CH3:4][CH:5]([CH2:16][CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])[CH2:6][CH2:7][O:8][C:9]1[CH:10]=[C:11](Br)[CH:12]=[CH:13][CH:14]=1.C[O:23][B:24]([O:27]C)[O:25]C.S(=O)(=O)(O)O>O1CCCC1>[CH3:4][CH:5]([CH2:16][CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])[CH2:6][CH2:7][O:8][C:9]1[CH:10]=[C:11]([O:23][B:24]([OH:27])[OH:25])[CH:12]=[CH:13][CH:14]=1
Reactant: COB(OC)OC
Reactant: CC(C)CCCC(C)CCOc1cccc(Br)c1
Agent: II
Agent: O=S(=O)(O)O
Agent: [Mg]
Solvent: C1CCOC1
Product: CC(C)CCCC(C)CCOc1cccc(OB(O)O)c1
Temperature: 25 °C
Yield: 74.5 %

Procedure:
Under an inert atmosphere, 7.5 g of magnesium and a small amount of iodine were charged in 100 ml of dried tetrahydrofuran in a three-necked flask. Using a dropping funnel, 90 g of the above-mentioned 3-(3,7-dimethyloctyloxy)-bromobenzene was dropped over 50 minutes. After completion of dropping, 200 ml of dried tetrahydrofuran was added, and the mixture was stirred while heating for 2 hours under reflux to prepare a Grignard reagent. After completion of heating, the reagent was left to cool to room temperature. Into a three-necked flask other than the above-mentioned flask was charged 38 g of trimethylboric acid and 300 ml of dried tetrahydrofuran, and the flask was cooled in a dry ice/aceton bath. Using a dropping funnel, the above-mentioned Grignard reagent solution was dropped over 35 minutes. After completion of dropping, the reaction solution was heated up to room temperature. The reaction solution was added to dilute sulfuric acid (sulfuric acid 12 ml/water 360 ml) and the mixture was stirred, then, bisected and the portions were extracted with 150 ml of ethyl acetate and 100 ml ethyl acetate, respectively. The organic layers were combined, then, trisected and respective portions were washed with 100 ml of water. The washed organic layers were combined and the solvent was distilled off by an evaporator, then, 100 ml of hexane was added to suspend a solid component and the suspension was filtrated. Further, the filtrated substance was washed with 100 ml of hexane. 63 g of 3-(3,7-dimethyloctyloxy)-phenylboric acid was obtained in the form of while solid. Under an inert atmosphere, into a three-necked flask was charged 60 g of the above-mentioned 3-(3,7-dimethyloctyloxy)-bromobenzene, 250 ml of toluene, 250 ml of water, 62 g of potassium carbonate and 1.2 g of tetrakis(triphenylphosphine)palladium complex. Argon was bubbled through the solution for 20 minutes to remove oxygen, then, 63 g of the above-mentioned 3-(3,7-dimethyloctyloxy)-phenylboric acid was added and the mixture was heated up to 90° C., and stirred for 8 hours while heating at the same temperature. After completion of heating, the mixture was left to cool to room temperature. The toluene layer was separated, then, a colored component was removed by silica gel column chromatography. The solvent was distilled off to obtain 98 g of an oily product. This is referred to as compound G.
Reaction SMILES: C(OCCOCCO)CCC.[BH4-].[Na+].[O:14](C)[C:15]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])=O.S(=O)(=O)(O)O>C1(C)C(C)=CC=CC=1>[CH2:15]([OH:14])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25]
Reactant: CCCCCCCCCC(=O)OC
Agent: O=S(=O)(O)O
Agent: [BH4-]
Agent: [Na+]
Solvent: Cc1ccccc1C
Solvent: CCCCOCCOCCO
Product: CCCCCCCCCCO
Temperature: 25 °C
Yield: 98 %

Procedure:
13.5 g (0.083 mole) of diethylene glycol monobutyl ether was added dropwise to a mixture consisting of 1.6 g (0.042 mole) of sodium borohydride, 10 ml of xylene and 5 g (0.027 mole) of methyl caprate at 95° C. over two hours while agitating the mixture. Subsequently, the mixture was agitated at the same temperature for two hours. After cooling to room temperature, the mixture was neutralized with dilute sulfuric acid. As a result, n-decanol was obtained in 98% yield.
Reaction SMILES: [Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([N:10]2[CH:19]=[CH:18][C:17]3[C:12](=[C:13]([F:23])[CH:14]=[C:15]([CH:20]4[CH2:22][CH2:21]4)[CH:16]=3)[C:11]2=[O:24])[C:3]=1[CH:4]=[O:5].CC(O)C.[BH4-].[Na+]>C(Cl)Cl>[Cl:1][C:2]1[C:3]([CH2:4][OH:5])=[C:6]([N:10]2[CH:19]=[CH:18][C:17]3[C:12](=[C:13]([F:23])[CH:14]=[C:15]([CH:20]4[CH2:22][CH2:21]4)[CH:16]=3)[C:11]2=[O:24])[CH:7]=[CH:8][CH:9]=1
Reactant: O=Cc1c(Cl)cccc1-n1ccc2cc(C3CC3)cc(F)c2c1=O
Agent: [BH4-]
Agent: [Na+]
Solvent: CC(C)O
Solvent: ClCCl
Product: O=c1c2c(F)cc(C3CC3)cc2ccn1-c1cccc(Cl)c1CO
Reaction time: 1 h
Yield: 86.2 %

Procedure:
2-chloro-6-(6-cyclopropyl-8-fluoro-1-oxoisoquinolin-2(1H)-yl)benzaldehyde (64.6 g, 0.19 mol) was dissolved in DCM (650 ml), then, IPA (325 ml) was added to the solution. At 4° C., NaBH4 (7.15 g, 0.19 mol) was added to the reaction mixture portion wise, then the resulting solution was stirred for 1 hr. The reaction was quenched by water (170 mL), then the mixture was filtered through Celite pad. DCM layer was collected by phase separation, and DCM was distilled out and IPA was added in the same time. The desired product was crystallized out from IPA, collected by filtration, and washed with cold IPA. The filter cake was dried under vacuum at 70° C. to afford 56.3 g of the title compound (86.6% isolated yield) as a white solid. MS (ESI) 343, 345 (M+H)+.
Reaction SMILES: [C:1]([O:5][C:6](=[O:14])[NH:7][C:8]1[S:9][C:10](Br)=[CH:11][N:12]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:15][Si:16]([C:19]#[CH:20])([CH3:18])[CH3:17].O>C(N(CC)CC)C.[Cu]I>[C:1]([O:5][C:6](=[O:14])[NH:7][C:8]1[S:9][C:10]([C:20]#[C:19][Si:16]([CH3:18])([CH3:17])[CH3:15])=[CH:11][N:12]=1)([CH3:4])([CH3:3])[CH3:2]
Reactant: CC(C)(C)OC(=O)Nc1ncc(Br)s1
Reactant: C#C[Si](C)(C)C
Agent: [Cu]I
Solvent: CCN(CC)CC
Solvent: O
Product: CC(C)(C)OC(=O)Nc1ncc(C#C[Si](C)(C)C)s1
Temperature: 80 °C
Yield: 79.1 %

Procedure:
(5-Bromo-thiazol-2-yl)-carbamic acid tert-butyl ester (2.0 g, 7.164 mmol) was taken in triethylamine (20 ml). To this solution was added CuI (0.041 g, 0.215 mmol), PdCl2 (PPh3)2 (0.050 g, 0.071 mmol) followed by the addition of trimethylsilylacetylene (1.055 g, 10.741 mmol). The reaction was heated at 80° C. overnight. Reaction mixture was cooled to room temperature and poured into water (50 ml), extracted with ethyl acetate (30 ml×3). The combined organic layer was washed with 1N HCl followed by brine and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The crude product was purified by column chromatography over silica gel using 6% ethyl acetate hexane as eluent to provide pure (5-trimethylsilanylethynyl-thiazol-2-yl)-carbamic acid tert-butyl ester (1.679 g).
Reaction SMILES: [C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:10][C:11]1[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][C:12]=1[N+:18]([O-:20])=[O:19].CCN(CC)CC>C(Cl)Cl>[O:17]([C:14]1[CH:15]=[CH:16][C:11]([CH3:10])=[C:12]([N+:18]([O-:20])=[O:19])[CH:13]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: OB(O)c1ccccc1
Reactant: Cc1ccc(O)cc1[N+](=O)[O-]
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: Cc1ccc(Oc2ccccc2)cc1[N+](=O)[O-]

Procedure:
Combine phenyl boronic acid (7.32 g, 60 mmol), 4-methyl-3-nitrophenol (4.5 g, 30 mmol), and Cu (oAC)2-H2O (6 g, 30 mmol) in 30 mL CH2Cl2 and treat with 6 g 4A molecular sieves powder. Add Et3N (15.18 g, 150 mmol) dropwise, and stir the reaction at ambient temperature for 8 days. Dilute with 100 mL CH2Cl2 and filter through celite and concentrate to dryness. Purification by chromatography using 2% EtOAc in hex anes gave the desired product as a yellow oil.
Reaction SMILES: COS(O)(=O)=O.B(OC)(OC)OC.C(=O)(OC)OC.C(OC)(=O)C.C[C:26]([O:28][CH2:29][C:30]1[CH2:39][S:38][C@@H:33]2[C@H:34]([NH2:37])[C:35](=[O:36])[N:32]2[C:31]=1[C:40]([OH:42])=[O:41])=O>>[NH2:37][CH:34]1[C:35](=[O:36])[N:32]2[C:31]([C:40]([OH:42])=[O:41])=[C:30]([CH2:29][O:28][CH3:26])[CH2:39][S:38][C@H:33]12
Reactant: CC(=O)OCC1=C(C(=O)O)N2C(=O)[C@@H](N)[C@H]2SC1
Agent: COB(OC)OC
Agent: COS(=O)(=O)O
Solvent: COC(=O)OC
Solvent: COC(C)=O
Product: COCC1=C(C(=O)O)N2C(=O)C(N)[C@H]2SC1
Temperature: 20 °C
Reaction time: 1 h
Yield: 83.8 %

Procedure:
11.9 g of a methanolic solution of methoxysulfonic acid (prepared as described in Preparation 2) and 3.11 g of trimethyl borate were added to a mixture of 25 ml of dimethyl carbonate and 5 ml of methyl acetate. The mixture was cooled to 20° C., and 2.74 g of 7-ACA were added thereto, followed by stirring at 20° C. for 1 hour. After completion of the reaction, the reaction mixture was treated following the procedures described in Example 2. 2.06 g (yield 84%) of the title compound in a highly pure form were produced.
Reaction SMILES: Br[C:2]1[N:6]2[N:7]=[CH:8][CH:9]=[CH:10][C:5]2=[N:4][CH:3]=1.[C:11]([Si:13]([CH3:16])([CH3:15])[CH3:14])#[CH:12].C(N(C(C)C)CC)(C)C>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH3:14][Si:13]([C:11]#[C:12][C:2]1[N:6]2[N:7]=[CH:8][CH:9]=[CH:10][C:5]2=[N:4][CH:3]=1)([CH3:16])[CH3:15]
Reactant: C#C[Si](C)(C)C
Reactant: Brc1cnc2cccnn12
Agent: [Cu]I
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Solvent: CCN(C(C)C)C(C)C
Solvent: CN(C)C=O
Product: C[Si](C)(C)C#Cc1cnc2cccnn12
Temperature: 25 °C
Reaction time: 1 h
Yield: 71.1 %

Procedure:
A mixture of 3-bromoimidazo[1,2-b]pyridazine (36.78 g, 0.186 mol; prepared according to Stanovnik, B. et al. Synthesis (1981), 12, 987-989), ethynyltrimethylsilane (21.89 g, 0.223 mol), Pd(PPh3)4 (10.73 g, 9.29 mmol), CuI (5.30 g, 0.028 mol), and diisopropylethylamine (32.4 mL, 0.279 mol) in 150 mL of DMF was stirred at ambient temperature, under an atmosphere of N2, for 1 h. The reaction mixture was concentrated and the crude product was purified by silica gel flash chromatography (eluted with 0-5% MeOH/DCM) to provide 28.46 g of product.
Reaction SMILES: [CH:1]#[CH:2].[Cl:3][SiH:4]([CH2:6][SiH:7]([Cl:9])[Cl:8])[Cl:5]>>[Cl:3][Si:4]1([Cl:5])[CH:2]=[CH:1][Si:7]([Cl:9])([Cl:8])[CH2:6]1
Reactant: C#C
Reactant: Cl[SiH](Cl)C[SiH](Cl)Cl
Product: Cl[Si]1(Cl)C=C[Si](Cl)(Cl)C1
Reaction time: 3 h
Yield: 3.6 %

Procedure:
Hydrosilation of acetylene with bis(dichlorosilyl)methane in the presence of H2PtCl6. Into the same apparatus as described in Example 1 were placed 125 μl of a 0.1 M H2PtCl6 /IPA solution under a dry nitrogen atmosphere and the IPA removed under vacuum. Into the flask were added 3.01 g of bis(dichlorosilyl)methane and 20 ml of dried benzene. The flask content was heated to reflux temperature and acetylene gas was blown into the content at a rate of 90 ml/min for 3 hours. The reaction products were vacuum distilled at 67 Pa to yield a mixture comprising 1.99 g of 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-ene (TCD-GC area 3.6%); 1,1,3,3-tetrachloro-1,3-disilacyclopentane (TCD-GC area 47.4%); 1,1,3,3,6,6,8,8-octachloro-1,3,6,8-tetrasilaoctane (TCD-GC area 17.2%); and 1,1,3,3,6,6,8,8,11,11,13,13-dodecachloro-1,3,6,8,11,13-hexasilatridecane (TCD-GC area 8.6%). 1,1,3,3-Tetrachloro-1,3-disilacyclopent-4-ene=1H-NMR (CDCl3, ppm): 1.14 (s, 2H, SiCH2Si), 7.36 (s, 2H, CH=CH); 1,1,3,3 -tetrachloro-1,3-disilacyclopentane =1H-NMR (CDCl3, ppm): 1.12 (s, 2H, SiCH2Si), 1.50 (s, 4H, CH2CH2); and 1,1,3,3,6,6,8,8-octachloro-1,3,6,8-tetrasilaoctane=1H-NMR (CDCl3, ppm): 1.41-150 (m, 8H, SiCH2SiCH2CH2SiCH2Si), 5.71 (s, 2H, SiH).
Reaction SMILES: [C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[Na+].O.[N:11]1[C:18]([Cl:19])=[N:17][C:15](Cl)=[N:14][C:12]=1[Cl:13]>C1(C)C=CC=CC=1>[Cl:13][C:12]1[N:11]=[C:18]([Cl:19])[N:17]=[C:15]([O:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[N:14]=1
Reactant: Oc1ccccc1
Reactant: Clc1nc(Cl)nc(Cl)n1
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: Cc1ccccc1
Product: Clc1nc(Cl)nc(Oc2ccccc2)n1
Temperature: 50 °C
Reaction time: 1 h

Procedure:
An aqueous solution of 52 parts of phenol and 50 parts by volume of a 33% aqueous solution of sodium hydroxide in 250 parts of water is treated, at a temperature of between 30° and 35° C., with a solution of 92.5 parts of cyanuric chloride in 700 parts by volume of toluene, with thorough stirring. The reaction mixture is heated to 50° C. and stirred for a further 1 hour at this temperature. The organic phase is separated off and dried with magnesium sulfate and the bulk of the toluene is distilled off. The distillation residue is filtered off with strong suction and washed with twice 20 parts by volume of toluene. After drying under reduced pressure at 30° C., 80 parts of the compound 2,4-dichloro-6-phenoxy-1,3,5-triazine melting at 111 to 116° C. are obtained.
Reaction SMILES: N#N.Cl[C:4]1[N:9]=[N:8][C:7]([N:10]2[CH2:15][CH2:14][CH:13]([N:16]([CH3:24])[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:12][CH2:11]2)=[C:6]([CH3:25])[C:5]=1[CH3:26].[F:27][C:28]1[CH:33]=[CH:32][C:31](B(O)O)=[CH:30][CH:29]=1.[F-].[Cs+]>O1CCOCC1>[F:27][C:28]1[CH:33]=[CH:32][C:31]([C:4]2[N:9]=[N:8][C:7]([N:10]3[CH2:15][CH2:14][CH:13]([N:16]([CH3:24])[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:12][CH2:11]3)=[C:6]([CH3:25])[C:5]=2[CH3:26])=[CH:30][CH:29]=1
Reactant: OB(O)c1ccc(F)cc1
Reactant: Cc1c(Cl)nnc(N2CCC(N(C)C(=O)OC(C)(C)C)CC2)c1C
Agent: N#N
Agent: [Cs+]
Agent: [F-]
Solvent: C1COCCO1
Product: Cc1c(-c2ccc(F)cc2)nnc(N2CCC(N(C)C(=O)OC(C)(C)C)CC2)c1C
Temperature: 95 °C
Yield: 86.8 %

Procedure:
Treat a N2 degassed mixture of tert-butyl 1-(6-chloro-4,5-dimethylpyridazin-3-yl)piperidin-4-yl(methyl)carbamate (3.01 g, 8.48 mmol), 4-fluorophenylboronic acid (1.23 g, 8.80 mmol) and CsF (4.08 g, 26.8 mmol) in 1,4-dioxane (80 mL) with (1,1′-bis(diphenylphosphino)ferrocene)palladium(II) chloride (1.10 g, 1.35 mmol). Heat the resulting mixture under N2 at 95° C. overnight. Partition the reaction mixture between H2O and EtOAc. Separate the layers, and wash the organic layer with brine. Dry the organic layer over Na2SO4, filter, and concentrate under reduced pressure. Purify the residue by flash silica gel chromatography (gradient of 20 to 80% EtOAc in hexanes) to provide the title compound (3.05 g, 87%). ES/MS m/z 415.2 (M+1).
Reaction SMILES: [CH2:1]([P+:3]([CH2:8]O)([CH2:6]O)[CH2:4]O)O.[Cl-:10].[CH3:11][NH:12][C:13]([NH:15][CH3:16])=[O:14].C1(C)C=CC=CC=1>O>[Cl-:10].[CH3:11][N:12]([CH2:8][P+:3]([CH2:1][N:12]([CH3:11])[C:13]([NH:15][CH3:16])=[O:14])([CH2:4][N:12]([CH3:11])[C:13]([NH:15][CH3:16])=[O:14])[CH2:6][N:12]([CH3:11])[C:13]([NH:15][CH3:16])=[O:14])[C:13]([NH:15][CH3:16])=[O:14]
Reactant: CNC(=O)NC
Reactant: OC[P+](CO)(CO)CO
Agent: [Cl-]
Solvent: Cc1ccccc1
Solvent: O
Product: CNC(=O)N(C)C[P+](CN(C)C(=O)NC)(CN(C)C(=O)NC)CN(C)C(=O)NC
Yield: 97.2 %

Procedure:
A mixture of THPC (9.53 g, 0.05 mol), 1,3-dimethylurea (17.62 g, 0.20 mol), and toluene (75 ml) was heated to reflux in an apparatus fitted with a Dean-Stark trap for azeotropic removal of the water. The mixture was held at reflux until the evolution of water ceased; 3.7 ml (0.20 mol) was collected in 1 hr., and no more passed over in the next hr. The product, which had separated during the reaction as a mass of white solids, was broken up, triturated under toluene, filtered, and dried, giving 22.88 g (97.2%) of tetrakis(1,3-dimethylureidomethyl)phosphonium chloride (I, R=R'=CH3, R"=H, X=Cl) as a white crystalline solid, mp 187°-189° C. dec. Two recrystallizations from 2-propanol (8 ml/g), followed by drying under vacuum for 2 hr at 56° C. (acetone), gave a 1:1 solvate of the product and 2-propanol, mp 194°-194.5° C. dec.