Name: 584-03-2|Butane-1,2-diol|99%
Brand: Ambeed
SKU: A539728
Price: 9.0 USD
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1
[ 106-88-7 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With water In N,N-dimethyl-formamide at 110℃; for 20h;
92.8%	With water at 90℃;
92.7%	With water at 90℃;	2 preparation of o-diol compounds (1) First, a C2-C16 monoolefin was used as a raw material, and a titanium silicate molecular sieve TS-1 having an MFI structure was used.HTS-1 as a catalyst, with an aqueous hydrogen peroxide solution as an oxidizing agent, according to the process disclosed in CN 104211665A,Oxidation to the corresponding hydrocarbon epoxide;(2) In a 100 ml jacketed stainless steel tubular reactor, 30 ml of a compound represented by the general formula (3)Substituted macroporous polystyrene season scale salt anion exchange resin catalyst, the catalyst bed at the bottom and end filled with inertball. The temperature of the reactor is controlled by an external circulation type heat transfer oil, and the reactor pressure is controlled by a back pressure valve installed on the outlet lineThe reaction material is passed through the bottom of the reactor through the bottom of the reactor and flows through the catalyst bed from the top of the reactor and is cooled by the coolerBut then flows into the reaction product tank. Time sampling, gas chromatography analysis reaction product composition. Study the concentration of reaction raw materials, reactionTemperature, pressure, liquid hourly space velocity and the type of catalyst on the reaction, the reaction materials used in Examples 1 to 10 are shown in Table1, the catalyst used has the general formula (3) structure, wherein Yi, 7, horses, 1? 6,1? 7 groups, resin crosslinking degree, resin alkali exchange capacitySee Table 2, the reaction process conditions and reaction results in Table 3. The catalyst represented by the general formula (3) has an ortho-halogenated styrene,Etine is prepared from the reaction starting material, the reaction equation is as follows:

92.5%	With water at 95℃;	2 In a 100 ml jacketed stainless steel tubular reactor, 30 ml of a halogen-substituted macroporous polystyrene quaternary ammonium salt type anion exchange resin catalyst having a structure represented by the general formula (3) was charged, and the upper and lower ends of the catalyst bed Filled with inert ceramic ball.The temperature of the reactor is controlled by an external circulation type heat transfer oil, which is controlled by a back pressure valve mounted on the outlet line. The reaction material is fed from the bottom of the reactor through the metering pump and flows through the catalyst bed from the top of the reactor , Cooled by the cooler and flowed into the reaction product tank.Time sampling, gas chromatography analysis reaction product composition.The reaction raw materials used in Examples 1 to 10 are shown in Table 1. The catalyst used has the structure of the general formula (3), wherein X and y are the same as those of the reaction formula, wherein the reaction temperature, pressure, liquid hourly space velocity and catalyst type change affect the reaction. , R5, R6, R7Group, resin crosslinking degree, resin alkali exchange capacity (dry basis) in Table 2, the reaction process conditions and reaction results in Table 3.The catalyst represented by the general formula (3) is prepared by preparing halogenated styrene and diene as reaction materials, and the reaction equation is as follows:
92.6%	With water at 85℃;	2 preparation of o-diol compound General procedure: In a 100 ml jacketed stainless steel tubular reactor, 30 ml of the structure represented by the general formula (3)Halogen meta-substituted macroporous polystyrene-divinylbenzene quaternary ammonium salt anion exchange resin catalyst,The catalyst bed is filled with an inert ceramic ball on the upper and lower ends.The temperature of the reactor is controlled by an external circulation type heat transfer oil,The reactor pressure is controlled by a back pressure valve mounted on the outlet line,The reaction material is fed from the bottom of the reactor through a metering pump,Flowing through the catalyst bed from the top of the reactor,Cooled by the cooler and flowed into the reaction product tank.Timing sampling,Analysis of the reaction product by gas chromatography.To investigate the reaction concentration,Reaction temperature, pressure,Liquid hourly space velocity and catalyst type change on the reaction,The reaction materials used in Examples 1 to 10 are shown in Table 1, and the catalyst used has the structure of the general formula (3), wherein the X, y, R5, R6, R7 groups, the ion exchange resin crosslinking degree, the alkali exchange capacity ) See Table 2, the reaction process conditions and reaction results in Table 3.
92.5%	With dihydrogen peroxide In water at 95℃; Molecular sieve;	2 preparation of vicinal diol compounds (1) The mono-olefins are first oxidized to the corresponding hydrocarbon epoxides according to the process disclosed in CN104211665A , with C2-C16 mono-olefins as starting material , then using a titanium silicalite sieve TS-1 or HTS-1 as a catalyst having an MFI structure and with an aqueous solution of hydrogen peroxide as an oxidizing agent.
90%	With fipronilβ-cyclodextrin In methanol; water at 40℃; for 12h;
	With sulfuric acid at 90℃;
	(acid hydrolysis);
	With sodium hydroxide
	With water; potassium carbonate In acetone at 60℃;
	Stage #1: ethyloxirane With titanium(IV) fluoride In chloroform-d1; dichloromethane at 80℃; Stage #2: With water In chloroform-d1; dichloromethane at 24.84℃; for 1h;
	With dihydrogen peroxide at 39.84℃; for 8h; Autoclave; Inert atmosphere;
	With tert.-butylhydroperoxide at 100℃; for 16h;
	With Sn-H-ZSM-35 zeolite In water at 39.84℃; for 6h; Autoclave; Inert atmosphere;
	With cobalt-salen complexes promoted on porous organic frameworks from 1,3,5-tris(3’-tert-butyl-4’-hydroxy-5’-formylphenyl)benzene and cyclohexanediamine In water at 40℃; for 3h; Autoclave;
	With epoxide hydrolase from Sphingomonas sp. HXN-200 Enzymatic reaction;
	With ECNU-21 In water at 59.84℃; for 8h; Autoclave;
11 %Spectr.	With water In dichloromethane at 20℃; for 24h;	8.1. Opening of 1,2-propoxide with D2O General procedure: The catalyst F-1 (0.011 g, 1.15 × 10-5 mol) was added to a solution of 1,2-propoxide (0.06 mL, 0.91 × 10-3 mol) in 1.5 mL of CH2Cl2 with stirring, then 3 mL of D2O was added, and the mixture stirred (700-1400 rpm) for 24 h at rt. Then the reaction mixture was left for a period of time to let the layers part. Then the layers were carefully separated and to the upper D2O layer was added t-BuOH (0.011 g, 1.48 × 10-4 mol). To the bottom CH2Cl2 layer was added (0.0047 g, 2.8 × 10-5 mol) of p-dinitrobenzene and a small portion was taken from the solution and diluted with CDCl3 . It was the sample used to estimate by 1H NMR the amount of the product in the layer (Figure S27). The same amount of p-dinitrobenzene was added to the middle layer followed by 1 mL of DMSO-d6 . Each solution was analyzed by 1H NMR. The upper layer contained 67% of the diol, the middle fraction had 15 % of the diol (Figure S28) and the bottom layer contained only 13 % of the initial epoxide (Figure S29). Total yield of 1,2-propanediol was 82 %.
	With water; hydrogen at 150℃; for 4h; Autoclave;

Reference： [1]Jiang, Jia-Li; Xiu, Zhuo; Hua, Ruimao [Synthetic Communications, 2008, vol. 38, # 2, p. 232 - 238]
[2]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN106478374, 2017, A Location in patent: Paragraph 0015; 0031; 0033; 0036
[3]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN106478373, 2017, A Location in patent: Paragraph 0024; 0025; 0026; 0028; 0029; 0030-0035
[4]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN106478375, 2017, A Location in patent: Paragraph 0027; 0029; 0030; 0036
[5]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN106478371, 2017, A Location in patent: Paragraph 0027-0028; 0032; 0037
[6]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN106478365, 2017, A Location in patent: Paragraph 0026-0027; 0029-0036
[7]Reddy, M. Anjun; Reddy, L. Rajender; Bhanumathi, N.; Rao, K. Rama [Organic Preparations and Procedures International, 2002, vol. 34, # 5, p. 537 - 540]
[8]Moureu; Dode [Bulletin de la Societe Chimique de France, 1937, vol. <5> 4, p. 287] Moureu; Dode; Dode [Memorial des Poudres, 1938, vol. 28, p. 263][Chemisches Zentralblatt, 1939, vol. 110, # II, p. 2398]
[9]Derbesy,M.; Naudet,M. [Bulletin de la Societe Chimique de France, 1968, p. 2962 - 2964]
[10]Jolley, Scott T.; Bradshaw, Jerald S. [Journal of Organic Chemistry, 1980, vol. 45, # 18, p. 3554 - 3559]
[11]Lu; Hu; Osmond; Patrick; James [Canadian Journal of Chemistry, 2001, vol. 79, # 8, p. 1201 - 1206]
[12]Location in patent: experimental part Marchetti, Fabio; Pampaloni, Guido; Biancalana, Lorenzo [Inorganica Chimica Acta, 2012, vol. 385, p. 135 - 139]
[13]Tang, Bo; Dai, Weili; Wu, Guangjun; Guan, Naijia; Li, Landong; Hunger, Michael [ACS Catalysis, 2014, vol. 4, # 8, p. 2801 - 2810]
[14]Acharya, Sitaram; Hanna, Tracy A. [Polyhedron, 2016, vol. 107, p. 113 - 123]
[15]Dai, Weili; Wang, Chuanming; Tang, Bo; Wu, Guangjun; Guan, Naijia; Xie, Zaiku; Hunger, Michael; Li, Landong [ACS Catalysis, 2016, vol. 6, # 5, p. 2955 - 2964]
[16]Zhong, Mingmei; Li, He; Chen, Jian; Tao, Lin; Li, Can; Yang, Qihua [Chemistry - A European Journal, 2017, vol. 23, # 48, p. 11504 - 11508]
[17]Zhang, Jian-Dong; Yang, Xiao-Xiao; Jia, Qiao; Zhao, Jian-Wei; Gao, Li-Li; Gao, When-Chao; Chang, Hong-Hong; Wei, Wen-Long; Xu, Jian-He [Catalysis science and technology, 2019, vol. 9, # 1, p. 70 - 74]
[18]Liu, Xue; Mao, Wenting; Jiang, Jingang; Lu, Xinqing; Peng, Mingming; Xu, Hao; Han, Lu; Che, Shun-ai; Wu, Peng [Chemistry - A European Journal, 2019, vol. 25, # 17, p. 4520 - 4529]
[19]Belokon, Yuri N.; Dmitrienko, Artem O.; Gak, Alexander S.; Gerasimov, Igor S.; Kuznetsova, Svetlana A.; Larionov, Vladimir A.; Li, Han; Medvedev, Michael G.; Nelyubina, Yulia V.; North, Michael; Saghyan, Ashot S.; Smol'yakov, Alexander F.; Zhereb, Vladimir P. [Beilstein Journal of Organic Chemistry, 2020, vol. 16, p. 1124 - 1134]
[20]Deng, Qiang; Deng, Shuguang; Gao, Ruijie; Li, Xiang; Tsang, Shik Chi Edman; Wang, Jun; Zeng, Zheling; Zou, Ji-Jun [Journal of the American Chemical Society, 2021, vol. 143, # 50, p. 21294 - 21301]

2
[ 106-98-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 1-butylene With potassium peroxomonosulfate; potassium chloride In water monomer; acetone at 30℃; for 12h; Large scale; Stage #2: With water monomer; potassium hydroxide at 25 - 40℃; for 4h; Large scale;	2 Example 2 In a 100 L reactor, 50 kg of water, 10 kg of acetone, 44 kg of potassium peroxodisulfate complex salt (oxone, 0.071 Kmol), potassium chloride 6.3 kg (0.11 Kmol) and 1-butene 4 kg (56.11, 0.071 Kmol) were added and heated. Stirring reaction to 30 ° C for 12 h, after the reaction is completed, reduce the temperature to 25 ° C, add 20% potassium hydroxide aqueous solution to adjust the pH to 12, heat to 40 ° C, stirMix reaction for 4h. After the reaction, it was cooled to room temperature, kept strong alkaline, extracted with dichloromethane to remove impurities, and then adjusted to pH 2 with 6 mol/L hydrochloric acid. The product was extracted with ethyl acetate, and the solvent was evaporated to give 1,2-butanediol. 5.65 kg, yield 88%.
	With dihydrogen peroxide; tungsten(VI) oxide; acetic acid at 70℃;
	With formic acid; dihydrogen peroxide at -17℃; beim anschliessenden Erwaermen mit wss. Natronlauge;

	With potassium permanganate In water monomer
	With dihydrogen peroxide In methanol at 80℃; for 10h; Autoclave;	2 2. Preparation of o-diol compounds General procedure: In a 500ml autoclave, a solvent, an olefin, an oxidant and a particulate titanium silicalite catalyst are distributed, and the catalyst is fixed on the side of the cooling coil of the autoclave by a hanging basket.After the completion of the feeding, nitrogen was flushed into the reaction vessel to set the initial pressure of the reaction, and the stirring was started to examine the effects of different olefin raw materials, solvents, temperature, pressure, reaction time, feed ratio, and catalyst on the reaction.After the reaction started, the oxidant partially decomposed, so the reactor pressure gradually increased.After the reaction was terminated, sampling was carried out, and the product composition was analyzed by gas chromatography.The reaction olefin raw materials used in Examples 1 to 10 are shown in Table 1.The catalyst titanium silicate molecular sieve raw powder, the nano SiO2 and the heteropoly acid mass distribution used in the examples, the titanium silicon molar ratio in the titanium silicon molecular sieve raw powder,Reaction charge molar ratio, solvent, oxidant mass concentration,The types of heteropolyacids are shown in Table 2.The batch reaction process conditions and results are shown in Table 3.The conditions and results of the continuous bed continuous reaction process are shown in Table 4.
	With diboron trioxide; γ-Al₂O₃; dihydrogen peroxide In methanol at 70℃; for 6h; Molecular sieve;
	Stage #1: 1-butylene With 3-chloro-benzenecarboperoxoic acid In water monomer at 0 - 20℃; Inert atmosphere; Stage #2: With sulfuric acid; water monomer Inert atmosphere;
	With dihydrogen peroxide In ethanol; butanone at 100℃; Molecular sieve;	3 Example 3 100 g of titanium-silicon molecular sieves were loaded into the slurry bed reactor, the total liquid volume was 2 liters, and the catalyst loading accounted for 5% of the total liquid. The molar ratio of butanone, ethanol and hydrogen peroxide is 60:30:1, the mass concentration of hydrogen peroxide is 70%, the mol ratio of 1-butene and hydrogen peroxide is 0.5:1, butanone, ethanol and hydrogen peroxide are injected into the reactor with metering pump respectively, 1-butane The alkene is injected into the reactor through a metering pump, and the feed is contacted and reacted with a shaped catalyst containing titanium-silicon molecular sieve to synthesize 1,2-butanediol. Reaction conditions: the reaction temperature is 100°C, the reaction pressure is 3MPa, and the liquid space velocity of the reaction bed is 0.1h-1. The obtained product was analyzed, and the selectivity of 1,2-butanediol was 95.1%, and the conversion rate of hydrogen peroxide was 98.2%.

Reference： [1]Current Patent Assignee: HUAIHUA UNIVERSITY - CN109384641, 2019, A Location in patent: Paragraph 0030; 0031
[2]Mugdan; Young [Journal of the Chemical Society, 1949, p. 2991,2993,2999]
[3]Criegee et al. [Justus Liebigs Annalen der Chemie, 1956, vol. 599, p. 81,93]
[4]Puchkov; Nepomnyashchikh, Yu. V. [Russian Journal of Physical Chemistry, 2017, vol. 91, # 12, p. 2337 - 2343][Zh. Fiz. Khim., 2017, vol. 91, # 12, p. 2050 - 2056,7]
[5]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN107879898, 2018, A Location in patent: Paragraph 0034-0035; 0036-0037; 0039-0045
[6]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN107879897, 2018, A Location in patent: Paragraph 0032-0041
[7]Feng, Wei; Gao, Taotao; Lau, Kai Kiat; Lin, Yamei; Pan, Hui-Jie; Yang, Binmiao; Zhao, Yu [Angewandte Chemie - International Edition, 2021, vol. 60, # 34, p. 18599 - 18604][Angew. Chem., 2021, vol. 133, # 34, p. 18747 - 18752]
[8]Current Patent Assignee: HUNAN CHANGLING PETROCHEMICAL TECHNOLOGY DEVELOPMENT CO LTD - CN113773169, 2021, A Location in patent: Paragraph 0037-0028

3
[ 584-03-2 ]
[ 4417-81-6 ]
[ 5077-67-8 ]

Reference： [1]Acetylene Chemistry <New York 1949>S.119,

4
[ 108-24-7 ]
[ 584-03-2 ]
[ 13814-27-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With phosphorus pentoxide; silica gel at 20℃;
86%	With dmap; triethylamine In dichloromethane at 20℃; for 16h; Cooling with ice;	27 Preparation of 1,2-butanediol diacetate 1m Add 2.7 mL of 1,2-butanediol in a 200 mL round bottom bottle.15mL of triethylamine, 30mg of dimethylaminopyridine,100 mL of dichloromethane was slowly added dropwise with 10 mL of acetic anhydride under stirring in an ice bath.After the addition is complete, remove the ice bath.The system was stirred at room temperature for 16 hours.The reaction solution was washed with water, 1N hydrochloric acid,Wash with saturated sodium chloride solution and dry over anhydrous sodium sulfate.Concentrate to give the crude product.Finally, the product was separated by column chromatography (petroleum ether: ethyl acetate = 10:1).The isolated yield was 86%.
73%	With sulfuric acid for 0.25h; Heating;

With pyridine

Reference： [1]Eshghi, Hossein; Shafieyoon, Parvaneh [Journal of Chemical Research, 2004, # 12, p. 802 - 805]
[2]Current Patent Assignee: SHANGHAITECH UNIVERSITY - CN108707096, 2018, A Location in patent: Paragraph 0087; 0088; 0089
[3]Poppe, Laszlo; Novak, Lajos; Kajtar-Peredy, Maria; Szantay, Csaba [Tetrahedron Asymmetry, 1993, vol. 4, # 10, p. 2211 - 2218]
[4]Wahler, Denis; Boujard, Olivier; Lefèvre, Fabrice; Reymond, Jean-Louis [Tetrahedron, 2004, vol. 60, # 3, p. 703 - 710]

5
[ 18162-48-6 ]
[ 584-03-2 ]
[ 136984-23-1 ]

Yield	Reaction Conditions	Operation in experiment
86%	With N-ethyl-N,N-diisopropylamine In diethyl ether at 0 - 20℃; Inert atmosphere;
84%	With triethylamine In dichloromethane at 0 - 20℃;
84.1%	With triethylamine In dichloromethane at 20℃; for 16h; Inert atmosphere;

80%	With 1H-imidazole In dichloromethane at -40 - 20℃; for 3.5h;	Preparation of 1-(tert-butyldimethylsilyloxy)butan-2-olA round bottom flask was charged with t-butyldimethylsilyl chloride (418mg, 2.77mmol), imidazole (227mg, 3.33mmol) and dissolved in dichloromethane (20ml_). The reaction mixture was cooled to -40°C and a solution of 1 ,2-butanediol (250 mg in 10 ml_ of dichloromethane) was added dropwise to the previously formed solution. The reaction was stirred 30 minutes at that temperature before warming it up to room temperature and stirred for an additional 3 hours. The reaction mixture was filtered to removed imidazole hydrochloride that had formed. The residue was purified by flash column chromatography (S1O2 (dry loaded), 5-20% ethyl acetate / heptane) to provide 1-(tert-butyldimethylsilyloxy)butan-2-ol (450mg, 80%) as a colorless oil. 1H NMR (400 MHz, CDCI3) δ ppm 0.03 - 0.09 (m, 6 H), 0.88 - 0.90 (m, 9 H), 0.95 (t, J=7.52 Hz, 3 H), 1.37 - 1.49 (m, 2 H), 2.39 (br. s., 1 H), 3.39 (dd, J=9.67, 7.33 Hz, 1 H), 3.55 (m, J=9.65, 6.67, 3.37, 3.37 Hz, 1 H), 3.62 (dd, J=9.77, 3.32 Hz, 1 H).
45%	With 1H-imidazole In N,N-dimethyl-formamide for 10h;
45%	With 1H-imidazole In DMF (N,N-dimethyl-formamide) for 10h;	3A Synthesis of (+/-)-1-tert-butyldimethylsilyloxy-2-hydroxybutane EXAMPLE 3A Synthesis of (+-)-1-tert-butyldimethylsilyloxy-2-hydroxybutane A 50 mL round bottom flask was charged with (+-)-1,2-butanediol (1 g, 11.09 mmol) and to it was added dimethylformamide (8 mL) followed by tert-butyldimethylsilyl chloride (2.5 g, 16.64 mmol) and imidazole (1.88 g, 27.7 mmol). The reaction mixture was stirred for 10 hours after which it was diluted with dichloromethane and poured into a separatory finnel and washed with water (80 mL) and brine and dried over magnesium sulfate. After filtration and concentration the crude oil was purified by silica gel flash chromatography (hexanes:ethylacetate) to obtain 1 gm of pure desired product in 45% yield. 1H (CDCl3) δ (ppm): 3.6 (m, 1H), 3.5 (m, 1H), 3.4 (m, 1H), 2.4 (s, 1H), 1.44 (m, 2H), 0.99 (t, 3H), 0.9 (s, 9H), 0.06 (s, 6H).
45%	With 1H-imidazole In N,N-dimethyl-formamide for 10h;	3A Synthesis of (±)-1 -tert-butyldimethylsilyloxy-2-hy- droxybutane A 50 mE round bottom flask was charged with (±)-1,2- butanediol (1 g, 11.09 mmol) and to it was added dimethylformamide (8 mE) followed by tert-butyldimethylsilyl chlo25 ride (2.5 g, 16.64 mmol) and imidazole (1.88 g, 27.7 mmol).The reaction mixture was stirred for 10 hours after which it was diluted with dichloromethane and poured into a separatory thnnel and washed with water (80 mE) and brine anddried over magnesium sulfate. Afier filtration and concentra30 tion the crude oil was purified by silica gel flash chromatography (hexanes:ethylacetate) to obtain 1 gm of pure desiredproduct in 45% yield. ‘H (CDC13) ö(ppm): 3.6 (m, 1H). 3.5 (m, 1H), 3.4 (m, 1H), 2.4 (s, 1H), 1.44 (m, 2H), 0.99 (t, 3H), 0.9 (s, 9H), 0.06 (s, 6H).
18%	With 1H-imidazole In dichloromethane at 25℃;	30.1 Step 1 : To a solution of 1,2-butanediol (3 g, 33.3 mmol, 1.0 eq) in DCM (30 mL) at 0 °C was added TBSC1 (7.5 g, 50.0 mmol, 1.5 eq) and imidazol (6.8 g, 100.0 mmol, 3 eq). The mixture was stirred at 25 °C overnight before it was concentrated under reduced pressure.The residue was diluted with water (30 mL) and extracted with EtOAc (3 x 30 mL). The combined organic layer was washed with brine, dried over NaiSCL, concentrated. The residue was purified by flash column chromatography on silica gel (petroleum ethenEtOAc =5: 1) to give l-((tert-butyldimethylsilyl)oxy)butan-2-ol (1.2 g, 18% yield).
	With 1H-imidazole In dichloromethane 0 deg C up to RT;
	With 1H-imidazole In dichloromethane at 0 - 20℃; Inert atmosphere;

Reference： [1]Dzieszkowski, Krzysztof; Rafiński, Zbigniew [Advanced Synthesis and Catalysis, 2020, vol. 362, # 18, p. 3830 - 3835]
[2]Gharpure, Santosh J.; Shukla, Manoj K.; Vijayasree [Organic Letters, 2009, vol. 11, # 23, p. 5466 - 5469]
[3]Burns, Michael J.; Thatcher, Robert J.; Taylor, Richard J. K.; Fairlamb, Ian J. S. [Dalton Transactions, 2010, vol. 39, # 43, p. 10391 - 10400]
[4]Current Patent Assignee: PFIZER INC - WO2011/158149, 2011, A1 Location in patent: Page/Page column 83-84
[5]Location in patent: experimental part Purohit, Ajay; Radeke, Heike; Azure, Michael; Hanson, Kelley; Benetti, Richard; Su, Fran; Yalamanchili, Padmaja; Yu, Ming; Hayes, Megan; Guaraldi, Mary; Kagan, Mikhail; Robinson, Simon; Casebier, David [Journal of Medicinal Chemistry, 2008, vol. 51, # 10, p. 2954 - 2970]
[6]Current Patent Assignee: LANTHEUS MI HOLDINGS INC - US2005/191238, 2005, A1 Location in patent: Page/Page column 18
[7]Current Patent Assignee: LANTHEUS MI HOLDINGS INC - US9408927, 2016, B2 Location in patent: Page/Page column 36
[8]Current Patent Assignee: NANJING IMMUNOPHAGE BIOTECH - WO2020/186220, 2020, A1 Location in patent: Paragraph 0158
[9]Hale; Bhatia; Peak; Manaviazar [Tetrahedron Letters, 1993, vol. 34, # 33, p. 5343 - 5346]
[10]Hale, Karl J.; Manaviazar, Soraya; George, Jonathan H.; Walters, Marcus A.; Dalby, Stephen M. [Organic Letters, 2009, vol. 11, # 3, p. 733 - 736]

6
[ 98-59-9 ]
[ 584-03-2 ]
[ 143693-24-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With di(n-butyl)tin oxide In dichloromethane at 0 - 20℃;
82%	With di(n-butyl)tin oxide; triethylamine In dichloromethane at 0 - 20℃; for 4h;	228C Example 228C: 2-hydroxybutyl 4-methylbenzene-1-sulfonate A vial containing a solution of butane-1,2-diol (0.500 g, 5.55 mmol) in dichloromethane (11 mL) was cooled to 0 °C. Next, dibutylstannanone (0.028 g, 0.11 mmol) and 4- methylbenzene-1-sulfonyl chloride (1.07 g, 5.60 mmol) were added, followed by triethylamine (0.81 mL, 5.8 mmol). The cooling bath was removed, and the vial was allowed to warm to ambient temperature. After 4 hours, the reaction mixture was poured into 1 M hydrochloric acid (30 mL) and extracted with dichloromethane (3 × 20 mL). The organic phases were combined and washed sequentially with water, saturated aqueous sodium bicarbonate, and brine. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified using silica gel chromatography [40 g column, 0-50% gradient of ethyl acetate in heptanes) to give the title compound (1.11 g, 4.54 mmol, 82% yield). 1H NMR (400 MHz, CDCl3) δ ppm 7.80 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 4.04 (dd, J = 10.1, 3.1 Hz, 1H), 3.90 (dd, J = 10.1, 7.0 Hz, 1H), 3.82 - 3.72 (m, 1H), 2.45 (s, 3H), 2.09 (d, J = 4.8 Hz, 1H), 1.47 (dd, J = 7.9, 6.6 Hz, 2H), 0.94 (d, J = 7.4 Hz, 3H).
80%	With triethylamine In dichloromethane at 20℃; for 16h; Inert atmosphere;	1-Toluenesulfonyloxybutan-2-ol (5d) A solution of toluenesulfonyl chloride (51.5 g, 270 mmol, 1 eq.), triethylamine (54.6 g, 405 mmol, 1.5 eq.) and butane-1,2-diol (36.5 g, 540 mmol, 2 eq.) under nitrogen in dichloromethane (800 mL), was stirred at 20 °C for 16 h. The reaction was then quenched with ice cold water (550 mL) and the aqueous layer removed. The organic layer was then washed sequentially with ice-cold 2 M HCl (550 mL), sat. NaHCO3 (550 mL) and brine (550 mL). The organic phase was then dried over MgSO4, filtered and concentrated in vacuo to afford the crude material. The product was purified via flash column chromatography (10 % EtOAc in toluene) to afford a white crystalline powder (53 g, 80 %).

72%	With triethylamine
66%	With di(n-butyl)tin oxide; triethylamine In dichloromethane at 20℃; for 3h; Inert atmosphere;	2.1.3. (±)-2-Hydroxybutyl tosylate (2a) Under an argon atmosphere, to a catalytic amount of Bu2SnO (17.9 mg, 0.0719 mmol) were sequentially added a solution of (±)-S3a (300 mg, 3.33 mmol) in CH2Cl2 (3.9 mL), TsCl (637 mg, 3.34 mmol), and Et3N (0.50 mL, 3.60 mmol) at 0°C. After the mixture was stirred for 3 h at room temperature, the reaction was stopped with 2 M HCl. The products were extracted with CH2Cl2 (x3), and the combined organic layer was washed with H2O, sat. NaHCO3 aq (x2), and brine, then dried over Na2SO4. After evaporation in vacuo, the residue was purified by flash column chromatography on silica gel (hexane/AcOEt = 8/1→2/1) to give (±)-2a as a colorless oil (539 mg, 66%). All the spectroscopic data were in full agreement with those of the optically active compound, which was reported in the manuscript.
	With dmap In pyridine at 0℃; for 48h; Yield given;
	With pyridine	3 Production of (RS)-2-butanoyloxy-1-p-toluenesulfonyloxybutane 1b STR23 EXAMPLE 3 OF PRODUCTION OF THE SUBSTRATE Production of (RS)-2-butanoyloxy-1-p-toluenesulfonyloxybutane 1b STR23 Using 1,2-butanediol, pyridine and p-toluenesulfonyl chloride, (RS)-1-p-toluenesulfonyloxy-2-butanol 2b STR24 was prepared in the same manner as Example 1 of Production. Description: Colorless crystals. Melting point: 59°-60° C. 1 H NMR (90 MHz, CDCl3) δ (ppm): 0.79-1.05 (3H, t, CH3 CH2 --), 1.30-2.10 (2H, m, CH3 CH2 --), 2.15 (1H, d, OH), 2.45 (3H, s, CH3 --Ar), 3.60-4.12 (3H, m, --CH(OH)CH2 O--), 7.30, 7.76 (4H, 2d, Ar--H) Elemental analysis: Calcd. for C11 H16 O4 S: C, 54.08; H, 6.60. Found: C, 54.29; H, 6.75.

Reference： [1]Location in patent: scheme or table Gharpure, Santosh J.; Reddy, S. Raja Bhushan [Tetrahedron Letters, 2010, vol. 51, # 47, p. 6093 - 6097]
[2]Current Patent Assignee: ABBVIE INC; GOOGLE INC - WO2021/127499, 2021, A1 Location in patent: Page/Page column 342-343
[3]Burns, Michael J.; Ronson, Thomas O.; Taylor, Richard J. K.; Fairlamb, Ian J. S. [Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 1159 - 1165]
[4]Hamaguchi, Shigeki; Ohashi, Takehisa; Watanabe, Kiyoshi [Agricultural and Biological Chemistry, 1986, vol. 50, # 6, p. 1629 - 1632]
[5]Matsumoto; Oohana; Hashimoto; Usuda; Shimoda; Ohshima; Suzuki; Togawa [Tetrahedron, 2018, vol. 74, # 29, p. 3981 - 3988]
[6]Cvorakova, Hana; Holy, Antonin; Rosenberg, Ivan [Collection of Czechoslovak Chemical Communications, 1994, vol. 59, # 9, p. 2069 - 2094]
[7]Current Patent Assignee: KANEKA CORPORATION - US4745066, 1988, A

7
[ 201230-82-2 ]
[ 584-03-2 ]
1,2-butylene carbonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With N-chloro-succinimide; (neocuproine)Pd(OAc)2; sodium acetate In acetonitrile at 55℃; for 24h; Molecular sieve;
94%	With air; potassium iodide; palladium(II) iodide In ISOPROPYLAMIDE at 100℃; for 15h; Autoclave;
94%	With oxygen; potassium iodide; palladium(II) iodide In N,N-dimethyl acetamide at 100℃; for 15h;

	With triethylamine; copper dichloride 1.) THF, 30 kg/cm², 80 deg C, 4h, 2.) room temp, 18 h, 1 atm; Yield given. Multistep reaction;
	With oxygen; sodium carbonate; copper dichloride In acetonitrile at 100℃; for 3h; Autoclave;	3 Synthesis of 4-methyl-1,3-dioxolan-2-one General procedure: 2.2.1 Synthesis of 4-methyl-1,3-dioxolan-2-one :In a typical experiment the glass vial was charged with solvent (CH3CN, 9.0 mL), catalyst (CuCl2, 0.60 mmol), co-catalyst (Na2CO3, 0.60 mmol) and 1,2-PD (10 mmol). The vial was introduced into the autoclave which was sealed and charged with O2 (0.5 MPa) and CO up to a total pressure of 3 MPa.Under these conditions, also taking into account the free volume ofthe autoclave and the stoichiometry of the carbonylation process (Eq.(4)), the diol is thelimiting reagent. The autoclave was heated at 100◦C and allowed to react for 3 h.

Reference： [1]Pearson, David M.; Conley, Nicholas R.; Waymouth, Robert M. [Advanced Synthesis and Catalysis, 2011, vol. 353, # 16, p. 3007 - 3013]
[2]Location in patent: experimental part Gabriele, Bartolo; Mancuso, Raffaella; Salerno, Giuseppe; Ruffolo, Giuseppe; Costa, Mirco; Dibenedetto, Angela [Tetrahedron Letters, 2009, vol. 50, # 52, p. 7330 - 7332]
[3]Location in patent: experimental part Gabriele, Bartolo; Mancuso, Raffaella; Salerno, Giuseppe; Veltri, Lucia; Costa, Mirco; Dibenedetto, Angela [ChemSusChem, 2011, vol. 4, # 12, p. 1778 - 1786]
[4]Mizuno, Takumi; Nakamura, Fumikazu; Egashira, Yoshitaka; Nishiguchi, Ikuzo; Hirashima, Tsuneaki; et al. [Synthesis, 1989, # 8, p. 636 - 638]
[5]Giannoccaro, Potenzo; Casiello, Michele; Milella, Antonella; Monopoli, Antonio; Cotugno, Pietro; Nacci, Angelo [Journal of Molecular Catalysis A: Chemical, 2012, vol. 365, p. 162 - 171]

8
[ 584-03-2 ]
[ 40348-66-1 ]

Reference： [1]Journal of the American Chemical Society,1984,vol. 106,p. 2687 - 2692
[2]Tetrahedron Asymmetry,1994,vol. 5,p. 239 - 246
[3]Advanced Synthesis and Catalysis,2003,vol. 345,p. 437 - 455

9
[ 584-03-2 ]
[ 73522-17-5 ]

Reference： [1]Agricultural and Biological Chemistry,1990,vol. 54,p. 1819 - 1827
[2]Chemistry Letters,1993,p. 2123 - 2124

10
[ 584-03-2 ]
[ 3347-90-8 ]

Reference： [1]Journal of Organic Chemistry,1985,vol. 50,p. 1992 - 1994

11
[ 584-03-2 ]
[ 5077-67-8 ]

Yield	Reaction Conditions	Operation in experiment
	With 1-hydroxytetraphenylcyclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)-mu-hydrotetracarbonyldiruthenium(II); cyclohexanone; at 150℃; for 0.5h;	1,2-butanediol (2.14 mmol), cyclohexanone (4.12 mmol), 1(2.3 mol), and 2 (3.6 mol) were combined in a NMR tube adaptedwith a J. Young valve and degassed by 5 ftp cycles. The mixture washeated to 150C for 19.5 h, after which the tube was cooled to rt,and a13C NMR spectrum recorded. The gas phase in the headspacewas analyzed by GC-TCD, and an aliquot of the liquid was dissolvedin DMSO-d6and the1H NMR spectrum recorded.

Reference： [1]Chemical Communications,2013,vol. 49,p. 5889 - 5891
[2]International Journal of Chemical Kinetics,2001,vol. 33,p. 310 - 316
[3]Tetrahedron,1991,vol. 47,p. 851 - 857
[4]European Journal of Organic Chemistry,2015,vol. 2015,p. 2960 - 2964
[5]Journal of Organic Chemistry,1986,vol. 51,p. 25 - 36
[6]Journal of Organic Chemistry,1991,vol. 56,p. 6233 - 6235
[7]Journal of Molecular Catalysis A: Chemical,2016,vol. 416,p. 81 - 87
[8]Catalysis science and technology,2019,vol. 9,p. 70 - 74

12
[ 584-03-2 ]
C₄H₉O₅P^(2-)*Ba⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With water-d2; phospho(enol)pyruvic acid mono potassium salt; adenosine 5'-triphosphate disodium salt; barium(II) chloride; magnesium chloride In various solvent(s) for 72h; Ambient temperature;

Reference： [1]Crans, Debbie C.; Whitesides, George M. [Journal of the American Chemical Society, 1985, vol. 107, # 24, p. 7008 - 7018]

13
[ 5077-67-8 ]
aluminium amalgam [ No CAS ]
[ 78-93-3 ]
[ 78-92-2 ]
[ 584-03-2 ]

Reference： [1]Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences,1905,vol. 140,p. 313
Bulletin de la Societe Chimique de France,1905,vol. <3>33,p. 325

14
[ 5077-67-8 ]
sodium amalgam [ No CAS ]
[ 78-93-3 ]
[ 78-92-2 ]
[ 584-03-2 ]

Reference： [1]Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences,1905,vol. 140,p. 313
Bulletin de la Societe Chimique de France,1905,vol. <3>33,p. 325

15
[ 584-03-2 ]
CuO [ No CAS ]
[ 4417-81-6 ]
[ 5077-67-8 ]

Reference： [1]Acetylene Chemistry <New York 1949>S.119,

16
[ 106-98-9 ]
[ 86943-35-3 ]
[ 123-38-6 ]
[ 5077-67-8 ]
[ 584-03-2 ]

Reference： [1]Physical Chemistry Chemical Physics,2000,vol. 2,p. 4029 - 4039

17
[ 98-88-4 ]
[ 584-03-2 ]
benzoic acid 2-hydroxybutyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine In toluene for 0.116667h; microwave irradiation;
15%	With triethylamine In toluene at 140℃; for 0.116667h; Cooling with ice;	1 COMPOUND 12: Benzoic acid 2-hydroxy-butyl ester Compound F Experimental Procedure: Step-1 To a solution of butane-1 ,2-diol 2 (20.0 g, 0.22 mol) in toluene (100 mL) was added trimethylamine (155 mL, 1 .1 1 mol) and benzoyl chloride (155.0 g, 1 .11 mol) at ice bath temperature. The reaction mixture was stirred at 140 °C over a period of 7 min. Reaction mixture was filtered to remove insoluble and concentrated under reduced pressure. The crude product obtained upon evaporation of volatiles under reduced pressure was purified by silica gel flash column chromatography using ethyl acetate/ hexane as an eluent to obtain the benzoic acid 2-hydroxy-butyl ester as a pale yellow oil (6.5 g, 15%).

Reference： [1]Caddick, Stephen; McCarroll, Andrew J; Sandham, David A [Tetrahedron, 2001, vol. 57, # 29, p. 6305 - 6310]
[2]Current Patent Assignee: KIMBERLY-CLARK CORP - WO2018/143911, 2018, A1 Location in patent: Page/Page column 24-25

18
[ 227626-60-0 ]
[ 584-03-2 ]
[ 925236-93-7 ]

Reference： [1]Archiv der Pharmazie,2005,vol. 338,p. 358 - 364

19
[ 584-03-2 ]
[ 86943-35-3 ]
[ 141-46-8 ]
[ 5077-67-8 ]

Reference： [1]Journal of Physical Chemistry A,2004,vol. 108,p. 7032 - 7037

20
[ 497-06-3 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
37%	With hydrogen In ethanol at 20℃; for 16h;	4 Example 4 [0064] Hydrogenation of 1,2-dihydroxy-3-butene. 1,2-Dihydroxy-3-butene (105 mg, 1.2 mmol) and 5% Pd/C (127 mg, 0.060 mmol Pd) were mixed with 10 mL absolute ethanol. The mixture was degassed and H2 (3.5 barg, approximately 50 psig) was added. After stirring for 16 h at ambient temperature the pressure was released. Pd/C was filtered off and solvent was removed in vacuo leaving a light yellow oil (40 mg, 0.44 mmol, 37% yield). 1H NMR analysis of the product indicates 1,2-dihydroxybutane. 1H NMR (CDCl3) ? 3.65 (m, 2H), 3.45 (m, 1H), 1.80 (br s, 2H), 1.45 (m, 2 H), 0.98 (t, 3H).

Reference： [1]Current Patent Assignee: EASTMAN CHEMICAL CO - US2004/44229, 2004, A1 Location in patent: Page 10

21
[ 5077-67-8 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen;dichloro[(R)-N-bis(3,4-difluorophenyl)phosphino-N-methyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine](triphenylphosphine)ruthenium; In methanol; at 20℃; under 16274.9 Torr; for 6h;Conversion of starting material;	Complex 5A-j from Example 12 (2.8 mg; 0.0025 mmol; 0.005 equiv) and 1hydroxy-2-butanone (45 muL; 0.5 mmol) were placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed methanol (5 mL) was added and the reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times. Analysis of the reaction mixture by chiral GC indicated 81.9percent conversion to 1,2-butanediol. The solvent was stripped and the residue was converted to the diacetate using acetic anhydride (0.14 mL; 1.5 mmol; 3 equiv) and triethylamine (0.28 mL; 2.0 mmol; 4 equiv) with a catalytic amount of DMAP in 2.5 mL of dichloromethane. Assay of the 1,2-diacetoxybutane thus produced indicated 87.4percent ee of the (R)-enantiomer according to chiral GC analysis. Chiral GC [30 m.x.0.25 mm Cyclosil-B (JW Scientific), 0.25 mum film thickness, 100° C. isothermal]: tR=7.23 min (1-hydroxy-2-butanone), tR=13.8, 14.1 min (1,2-butanediol), tR 16.85 min [(S)-1,2-diacetoxybutane], tR=17.75 min [(R)-1,2-diacetoxybutane].
	With hydrogen;dichloro[(R)-N-bis(3,4-difluorophenyl)phosphino-N-methyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine](triphenylphosphine)ruthenium; In ethanol; at 20℃; under 16274.9 Torr; for 6h;Conversion of starting material;	Complex 5A-j from Example 12 (2.8 mg; 0.0025 mmol; 0.005 equiv) and 1hydroxy-2-butanone (45 muL; 0.5 mmol) were placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (5 mL) was added and the reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times. Analysis of the reaction mixture by chiral GC indicated 93.4percent conversion to 1,2-butanediol. The solvent was stripped and the residue was converted to the diacetate using acetic anhydride (0.14 mL; 1.5 mmol; 3 equiv) and triethylamine (0.28 mL; 2.0 mmol; 4 equiv) with a catalytic amount of DMAP in 2.5 mL of dichloromethane. Assay of the 1,2-diacetoxybutane thus produced indicated 88.8percent ee of the (R)-enantiomer according to chiral GC analysis.
	With hydrogen;dichloro[(R)-N-bis(3,4-dichlorophenyl)phosphino-N-methyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine](triphenylphosphine)ruthenium; In methanol; at 20℃; under 16274.9 Torr; for 6h;Conversion of starting material;	Complex 5A-k from Example 13 (3.0 mg; 0.0025 mmol; 0.005 equiv) and 1hydroxy-2-butanone (45 muL; 0.5 mmol) were placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed methanol (5 mL) was added and the reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times. Analysis of the reaction mixture by chiral GC indicated 65.6percent conversion to 1,2-butanediol. The solvent was stripped and the residue was converted to the diacetate using acetic anhydride (0.14 mL; 1.5 mmol; 3 equiv) and triethylamine (0.28 mL; 2.0 mmol; 4 equiv) with a catalytic amount of DMAP in 2.5 mL of dichloromethane. Assay of the 1,2-diacetoxybutane thus produced indicated 84.6percent ee of the (R)-enantiomer according to chiral GC analysis.

Reference： [1]Patent: US6939981,2005,B1 .Location in patent: Page/Page column 20
[2]Patent: US6939981,2005,B1 .Location in patent: Page/Page column 20-21
[3]Patent: US6939981,2005,B1 .Location in patent: Page/Page column 23

22
[ 558-13-4 ]
[ 584-03-2 ]
[ 2482-57-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With triphenylphosphine In pyridine; ethyl acetate	1.B B. Carbontetrabromide (26.6 g, 80 mmol) and triphenylphosphine (21 g, 80 mmol) were added successively to 1,2-butanediol (7.2 g, 80 mmol) in anhydrous pyridine at 0° C., and the solution stirred at room temperature overnight. The mixture was concentrated and the residual oil dropwise added to vigorously stirred 1:5 ethyl acetate:hexanes (220 mL). The solution was decanted from the precipitate, concentrated, chromatographed (40 g silica gel, 1:3 ethyl acetate:hexanes), and gave GDLZ103 (11.5 g, 90%).

Reference： [1]Current Patent Assignee: GRIECO DESIGN HOLDINGS - US6048870, 2000, A

23
[ 591-18-4 ]
[ 7440-44-0 ]
[ 91-60-1 ]
[ 584-03-2 ]
3-bromophenyl 2-naphthyl sulphide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium carbonate In ethyl acetate; N,N-dimethyl-formamide	1 EXAMPLE 1 The butane-1,2-diol used as a starting material was obtained as follows: A mixture of 2-naphthalenethiol (3.2 g), 3-iodobromobenzene (6.7 g), potassium carbonate (1.4 g), cuprous chloride (0.4 g) and DMF (4 ml) was heated to reflux for 1 hour. The mixture was allowed to cool to ambient temperature and was partitioned between diethyl ether and water. The mixture was filtered and the organic layer was separated, dried (MgSO4) and evaporated. The residue was taken up in ethyl acetate, decolourised by treatment with charcoal, reisolated and purified by recrystallisation from methanol to give 3-bromophenyl 2-naphthyl sulphide (3.9 g, 65%), m.p. 68°-70° C.
65%	With potassium carbonate In ethyl acetate; N,N-dimethyl-formamide	1 EXAMPLE 1 The butane-1,2-diol used as a starting material was obtained as follows:- A mixture of 2-naphthalenethiol (3.2 g), 3-iodobromobenzene (6.7 g), potassium carbonate (1.4 g), cuprous chloride (0.4 g) and DMF (4 ml) was heated to reflux for 1 hour. The mixture was allowed to cool to ambient temperature and was partitioned between diethyl ether and water. The mixture was filtered and the organic layer was separated, dried (MgSO4) and evaporated. The residue was taken up in ethyl acetate, decolourised by treatment with charcoal, reisolated and purified by recrystallisation from methanol to give 3-bromophenyl 2-naphthyl sulphide (3.9 g, 65%), m.p. 68-70°C.

Reference： [1]Current Patent Assignee: AKZO NOBEL NV; ASTRAZENECA PLC - US5137913, 1992, A
[2]Current Patent Assignee: AKZO NOBEL NV; ASTRAZENECA PLC - EP409412, 1991, A2

24
[ 121-33-5 ]
[ 584-03-2 ]
vanillin-1,2-butylene glycol acetal [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94.3%	In water; toluene at 135℃; for 4h; Heating / reflux; with Dean-Stark tube;	2 Example 2[Synthesis of vanillin-1, 2-butylene glycol acetal (compound B) ]( Compound B ) Into a 300 ml reaction flask with a thermometer, a Dean-Stalk tube and a refluxing tube, 30.0 g of vanillin (molecular weight 152.15, 197.17 mmol) , 19.55 g of 1, 2-butylene glycol (molecular weight 90.12, 216.89 mmol), 150 mg of p-toluenesulfonic acid monohydrate (molecular weight 190.22, 789 μmol) , and 150 ml of toluene were charged, and the mixture was heated and refluxed in an oil bath at 1350C under nitrogen current. While removing formed water through the Dean-Stalk tube, the mixture was continuously refluxed. After heated for 4 hours, disappearance of raw materials was confirmed by the gas chromatogram. The reaction solution obtained was quenched in an aqueous sodium carbonate solution, extracted with toluene, washed with salt water, and dried with dehydrated sodium sulfate . After filtration, the solvent in the extract solution was removed by rotary evaporator and subjected to vacuum distillation to obtain an aimed compound, vanillin-1, 2-butylene glycol acetal EPO in form of a colorless transparent oil. The production amount was 41.7O g (molecular weight 224.26, 185.93 mmol) ; the purity was 100% (isomer ratio 53.7 : 46.3); the yield was 94.3%; and the boiling point was 127 to 129°C (30 to 32 Pa) .1H-NMR (500MHz, CDCl3, δ) ppm: 0.99-1.05 (m, 3H) , 1.56-1.83 (m, 2H), 3.63 (t, J=7.1 Hz, 0.4H), 3.71 (t, J=7.1 Hz, 0.6H), 3.92 (s, 3H), 4.09 (t, J=7.1 Hz, 0.6H), 4.12-4.21 (m, IH), 4.24-4.30 (m, 0.4H), 5.67-5.69 (m, IH), 5.75 (s, 0.6H), 5.84 (s, 0'.4H), 6.89-6.93 (m, IH), 6.97-7.03 (m, 2H).IR (membrane) cm"1: 3412, 2966, 2879, 1611, 1519, 1464, 1436, 1405, 1370, 1277, 1241, 1165, 1078, 1032, 956, 860, 823, 779. •MS (m/e) : 224 (M+), 207, 195, 169, 165, 151, 137, 124, 101, 93, 81, 65, 55, 39.

Reference： [1]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - WO2007/4740, 2007, A1 Location in patent: Page/Page column 30-31

25
[ 56-81-5 ]
[ 57-55-6 ]
[ 513-85-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
43%	With sodium hydroxide; hydrogen at 202℃;	4; 5; 6 Examples 4-7 describe methods to reduce the formation of four- carbon product BDO and maximize the conversion of polyhydric alcohol glycerol to three-carbon product propylene glycol with a solid phase catalyst such as the "G" catalyst as disclosed in US 6,479,713 or the "HC-1" catalyst available from Sd Chemie (Louisville, KY). Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 3. The effect of the concentration of alkali (sodium hydroxide) in the feed at constant temperature and constant LHSV on the amount of BDO formed was investigated. Higher levels of sodium hydroxide resulted in greater formation of BDOs, thus, the formation of BDOs was minimized when the reaction was operated at lower concentrations (1- 1.9 wt %) of alkali promoter (Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4).
33.2%	With sodium hydroxide; hydrogen at 154 - 229℃;	1 EXAMPLE 1.; A series of studies were conducted in a 2000ml high-pressure Stainless Steel 316 reactor. A solid catalyst similar to the "G" catalyst disclosed in US 6,479,713 or the "HC-1 " catalyst available from Sd Chemie (Louisville, KY) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5hr"1 to 2.5hr'1. Hydrogen was supplied at 1200-1600 psi EPO (about 83-110 bar) and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1 :1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. EPO
27%	With sodium hydroxide; hydrogen at 196℃;	3 Stainless Steel 316 reactor. As described in Figure 10, a solid catalyst was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of pure glycerol was fed through the catalyst bed at LHSV ranging from 0.5hr"1 to 2.5hr'1. Hydrogen was supplied at 1200 to 1600 psi (82.7 to 110.3 bar) and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 1 : 1 to 10: 1 , such as at 5: 1.Table 4 describes the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the three-carbon compound glycerol was converted and between 36.3-55.4% of the three-carbon compound propylene glycol was recovered. In addition to propylene glycol, the reaction product contained 0.04-2.31% of the four-carbon butanediol compounds and other non- PG diols, which were recovered from the reaction product (Table 3).

10%	With sodium hydroxide; hydrogen In water at 150 - 210℃;	2.25; 2.5; 2.6; 2.27; 2.16; 2.16; 2.26; 2.21; 2.9; 3.6; 3.21; 3.25; 3.16; 3.5; 3.26; 3.27; 3.9; 4.25; 4.6; 4.16; 4.21; 4.5; 4.27; 4.26; 4.9 EXAMPLE 2; Example 2 describes a method to reduce the formation of BDOs and maximize the conversion of glycerol to propylene glycol with a solid phase catalyst such as the “G” catalyst as disclosed in U.S. Pat. No. 6,479,713 or the “HC-1” catalyst available from Sud Chemie (Louisville, Ky.). Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. Table 7 in FIG. 4 describes the conditions used in this Example, and discloses the products produced in this Example.; EXAMPLE 3; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Table 8 in FIG. 5 describes the conditions used in this Example, and discloses the products produced in this Example.; EXAMPLE 4; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Table 9 in FIG. 6 describes the conditions used in this Example, and discloses the products produced in this Example.
	With sodium hydroxide; hydrogen In water at 159 - 212℃;	6.D16-M-423-01; 6.D16-M-423-02; 6.D16-M-423-03; 6.D16-M-423-04; 6.D16-M-423-05; 6.D16-M-423-06; 6.D16-M-423-07; 6.D16-M-424-01; 6.D16-M-424-02; 6.D16-M-424-05; 6.D16-M-425-01; 6.D16-M-425-02; 6.D16-M-425-03; 6.D16-M-425-04; 6.D16-M-425-05; 6.D16-M-425-06 EXAMPLE 6; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1 except that 180 mL of Süd Chemie HC-1 catalyst was used. Table 11 in FIG. 8 describes the conditions used in this Example, and discloses the products produced in this Example.

Reference： [1]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - WO2008/133939, 2008, A1 Location in patent: Page/Page column 18-19; 25
[2]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - WO2008/57317, 2008, A1 Location in patent: Page/Page column 14-16
[3]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - WO2008/133939, 2008, A1 Location in patent: Page/Page column 18; 24
[4]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - US2008/103339, 2008, A1 Location in patent: Page/Page column 6
[5]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - US2008/103339, 2008, A1 Location in patent: Page/Page column 7

Yield	Reaction Conditions	Operation in experiment
		Example 7Synthesis of PGME Enriched Polyol Esters of Soy OilThis Example sets forth a representative synthesis of a propylene glycol monoester from a vegetable oil and the hydrogenolysis product mixture from the hydrogenolysis of sorbitol.Sorbitol was subjected to hydrogenolysis substantially as set forth in Example 1. The hydrogenolysis product was then subjected to distillation to remove the water. The compositions of the hydrogenolysis product before and after stripping are set forth in Table 7. TABLE 7 Composition of Hydrogenolysis Product Hydrogenolysis product Hydrogenolysis product Compound before stripping (wt %) after stripping (wt %) Sorbitol 6.2% 10.0% Xylitol 2.2% 3.5% Erthyritol 0.8% 1.3% Lactate 1.0% 1.6% Glycerol 10.9% 17.6% <strong>[3068-00-6]1,2,4-Butanetriol</strong> 0.5% 0.8% Ethylene glycol 11.4% 18.4% Propylene glycol 22.3% 36.0% 2,3-Butanediol 1.4% 2.3% 1,3-Butanediol 1.0% 1.6% 1,2-Butanediol 2.5% 4.0% Ethanol 0.4% 0.6% Isopropanol 0.2% 0.3% Water 38.0% 0% Unknown 1.2% 1.9% A 1 liter autoclave reactor was charged with RBD soybean oil (refined, bleached, and deodorized soybean oil, 160 g), the hydrogenolysis product mixture from sorbitol (165 g), potassium acetate (0.08 g), and lithium hydroxide (0.02 g). The reactor headspace was purged with nitrogen. The reactor was pressurized with nitrogen at 350 psi and agitation at 800 rpm was began. The reaction mixture was heated to 240 C. over 1 hour at which time the pressure has increased to 550 psi. The reaction was held at 240 C. for 1.5 hours and then rapidly cooled to room temperature. The contents of the reactor were placed in a separatory funnel and neutralized with 0.5 g of conc. H3PO4, The mixture was extracted with hexanes and the organic layer was washed once with four times its volume of deionized water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator under reduced pressure to give a product having a Lovibond color of 2.9R., 14.0Y. The product composition was 60-81% propylene glycol monoester and 5% propylene glycol diester with an acid value of 21.6. This material may be used as a 100% biobased polyol ester replacement for petroleum derived PGMEs, for example as a coalescent in a latex paint formulation.

Yield	Reaction Conditions	Operation in experiment
		Example 8Candle Wax EstersThis Example sets forth a representative synthesis of a waxy propylene glycol monoester from a hydrogenated vegetable oil and the hydrogenolysis product mixture.A 1 L three neck round bottom flask was fitted with a heating mantle, a magnetic stirrer, a reflux condenser, and nitrogen sparge. Sorbitol was subjected to hydrogenolysis to obtain a hydrogenolysis product containing polyols (before stripping) and a composition as recited in Table 7, then heated under vacuum in a rotary evaporator to remove water and lower molecular weight alkyl monohydroxyl alcohols to obtain a stripped mixed polyol sorbitol hydrogenolysis product mixture (Table 7). The reaction vessel was charged with melted soy titer (fully hydrogenated soybean oil, 150 g) and the stripped mixed polyol mixture from the hydrogenolysis of sorbitol (30 g). The mixture was heated to 150 C. with agitation and NaOH (0.18 g) was added to catalyze alcoholysis of the melted soy titer by the polyol mixture. The mixture was heated from 150 C. to 220 C. with nitrogen sparging and good agitation over 1 hour. The product mixture enriched in fatty acid esters of polyols was then quickly cooled and neutralized with cone. H3PO4 (0.55 g). The cooled, neutralized product mixture separated into an upper phase containing the fatty acid esters of polyols and remaining titer esters and an aqueous bottom phase and the top phase solidified at room temperature. The solid top phase was collected and used in as a wax in a biobased candle wax formulation.

Yield	Reaction Conditions	Operation in experiment
		Example 6Sythesis of a Polyol EsterThis Example sets forth a representative synthesis of a polyol ester mixture from vegetable oils and the hydrogenolysis product mixture obtained by hydrogenolysis of sorbitol.A polyol sample (200 g) from the hydrogenolysis of sorbitol containing, by weight percent, 0.25% glucose; 0.25% xylose; 0.25% arabinose; 1.74% arabitol; 1.24% erythritol; 6.47% lactate; 10.45% glycerol; 1.00% 1,2,4-butanetriol; 42.54% ethylene glycol; 32.34% propylene glycol; 1.00% 2,3-butanediol; 0.5% 1,3-butanediol; and 2.00% 1,2-butanediol was combined with dried corn oil (200 g) and sodium inethoxide (1.0 g) in a 1000 mL round bottom flask. The mixture was heated with agitation at 120 C. for 4 hours. The product was cooled and neutralized with citric acid. Hexane was added and the organic layer was recovered. The hexane was removed from the product using a rotary evaporator under reduced pressure to give a residue of polyol esters of corn oil fatty acids, If desired, the product can be stripped using a wiped film evaporator/miiolecular still at 90 C., 0.6 millibars, 270 rpm and a flow rate of 4 mL/min. The resulting polyol ester composition is suitable for use as a 100% biobased replacement for a petroleum derived propylene glycol monoester.

29
[ 50-70-4 ]
[ 57-55-6 ]
[ 64-17-5 ]
[ 18826-95-4 ]
[ 3068-00-6 ]
[ 87-99-0 ]
[ 107-21-1 ]
[ 67-63-0 ]
[ 56-81-5 ]
[ 513-85-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide; hydrogen;nickel-rhenium-on-carbon; In water; at 220℃; under 31029.7 - 62059.4 Torr; for 4h;Product distribution / selectivity;	Example 7Synthesis of PGME Enriched Polyol Esters of Soy OilThis Example sets forth a representative synthesis of a propylene glycol monoester from a vegetable oil and the hydrogenolysis product mixture from the hydrogenolysis of sorbitol.Sorbitol was subjected to hydrogenolysis substantially as set forth in Example 1. The hydrogenolysis product was then subjected to distillation to remove the water. The compositions of the hydrogenolysis product before and after stripping are set forth in Table 7. TABLE 7 Composition of Hydrogenolysis Product Hydrogenolysis product Hydrogenolysis product Compound before stripping (wt %) after stripping (wt %) Sorbitol 6.2% 10.0% Xylitol 2.2% 3.5% Erthyritol 0.8% 1.3% Lactate 1.0% 1.6% Glycerol 10.9% 17.6% 1,2,4-Butanetriol 0.5% 0.8% Ethylene glycol 11.4% 18.4% Propylene glycol 22.3% 36.0% 2,3-Butanediol 1.4% 2.3% 1,3-Butanediol 1.0% 1.6% 1,2-Butanediol 2.5% 4.0% Ethanol 0.4% 0.6% Isopropanol 0.2% 0.3% Water 38.0% 0% Unknown 1.2% 1.9% A 1 liter autoclave reactor was charged with RBD soybean oil (refined, bleached, and deodorized soybean oil, 160 g), the hydrogenolysis product mixture from sorbitol (165 g), potassium acetate (0.08 g), and lithium hydroxide (0.02 g). The reactor headspace was purged with nitrogen. The reactor was pressurized with nitrogen at 350 psi and agitation at 800 rpm was began. The reaction mixture was heated to 240 C. over 1 hour at which time the pressure has increased to 550 psi. The reaction was held at 240 C. for 1.5 hours and then rapidly cooled to room temperature. The contents of the reactor were placed in a separatory funnel and neutralized with 0.5 g of conc. H3PO4, The mixture was extracted with hexanes and the organic layer was washed once with four times its volume of deionized water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator under reduced pressure to give a product having a Lovibond color of 2.9R., 14.0Y. The product composition was 60-81% propylene glycol monoester and 5% propylene glycol diester with an acid value of 21.6. This material may be used as a 100% biobased polyol ester replacement for petroleum derived PGMEs, for example as a coalescent in a latex paint formulation.

Reference： [1]Patent: US2008/103340,2008,A1 .Location in patent: Page/Page column 14-15

30
[ 50-70-4 ]
[ 6763-34-4 ]
[ 492-62-6 ]
[ 57-55-6 ]
[ 18826-95-4 ]
[ 3068-00-6 ]
[ 107-21-1 ]
[ 56-81-5 ]
[ 513-85-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide; hydrogen;nickel-rhenium-on-carbon; In water; at 220℃; under 31029.7 - 62059.4 Torr; for 4h;Product distribution / selectivity;	Example 5Polyester Polymerization ReactionThis Example sets forth a representative polyester polymerization reaction using a hydrogenolysis product mixture obtained by hydrogenolysis of glycerol or sorbitol according to certain embodiments disclosed herein.A composition enriched in compounds containing two hydroxyl groups was obtained by hydrogenolysis of glycerol by passing a 40% solution of crude glycerol obtained as a by-product of a palm biodiesel synthesis through a reactor substantially as set forth in Example 1. The reactor product was dewatered by distillation. A composite was prepared by combining four dewatered glycerol hydrogenolysis product samples to yield a mixture of polyols having the composition: 75.5% propylene glycol, 4.5% ethylene glycol, 1.8% lactic acid, 12.2% glycerol, and 0.5% water. This composition was subjected to short path distillation to reduce the water content to 0.15% and the undi stilled residue enriched in compounds containing two hydroxyl groups (Mixture 1) had the following composition: 75.8% propylene glycol, 4.7% ethylene glycol, 1.8% lactic acid, 1.3% 2,3-butanediol, and 13.8% glycerol.In one study, the composition enriched in compounds containing two hydroxyl groups is combined with an equimolar quantity of diisocyanate to make a predominantly linear polyurethane using the procedure set forth by Frisch (?Fundamental Chemistry and Catalysis of Polyirrethanes,? Frisch, K. C., in Polyurethane Technology, Paul Bruins, ed., Interscience Publishers, New York, 1969, the disclosure of which is incorporated in its entirety by reference herein).In a second study, the hydrogenolysis product from the hydrogenolysis of sorbitol containing, by weight percent, 0.25% glucose; 0.25% xylose; 0.25% arabinose; 1.74% arabitol; 1.24% erythritol; 6.47% lactate; 10.45% glycerol; 1.00% 1,2,4-butanetriol; 42.54% ethylene glycol; 32.34% propylene glycol; 1.00% 2,3-butanediol; 0.50% 1,3-butanediol; and 2.00% 1,2-butanediol is combined with a diisocyanate at 100 C. to make a branched polymer.The polymers resulting from study 1 and 2 will be suitable for use in fibers, hard and soft elastomers, coatings and adhesives, flexible and rigid foams, and thermoplastics and thermosetting plastics.; Example 6Sythesis of a Polyol EsterThis Example sets forth a representative synthesis of a polyol ester mixture from vegetable oils and the hydrogenolysis product mixture obtained by hydrogenolysis of sorbitol.A polyol sample (200 g) from the hydrogenolysis of sorbitol containing, by weight percent, 0.25% glucose; 0.25% xylose; 0.25% arabinose; 1.74% arabitol; 1.24% erythritol; 6.47% lactate; 10.45% glycerol; 1.00% 1,2,4-butanetriol; 42.54% ethylene glycol; 32.34% propylene glycol; 1.00% 2,3-butanediol; 0.5% 1,3-butanediol; and 2.00% 1,2-butanediol was combined with dried corn oil (200 g) and sodium inethoxide (1.0 g) in a 1000 mL round bottom flask. The mixture was heated with agitation at 120 C. for 4 hours. The product was cooled and neutralized with citric acid. Hexane was added and the organic layer was recovered. The hexane was removed from the product using a rotary evaporator under reduced pressure to give a residue of polyol esters of corn oil fatty acids, If desired, the product can be stripped using a wiped film evaporator/miiolecular still at 90 C., 0.6 millibars, 270 rpm and a flow rate of 4 mL/min. The resulting polyol ester composition is suitable for use as a 100% biobased replacement for a petroleum derived propylene glycol monoester.

Reference： [1]Patent: US2008/103340,2008,A1 .Location in patent: Page/Page column 14

31
[ 3068-00-6 ]
[ 110-63-4 ]
[ 18826-95-4 ]
[ 584-03-2 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 12675 - 12689

32
[ 95-54-5 ]
[ 584-03-2 ]
[ 29750-44-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With C₃₉H₃₁BMnNO₂P₂; potassium hydride In toluene at 150℃; for 36h;
94%	With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube;	2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent.
93%	With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube;

89%	With [Py(NP(iPr)₂)(NHP(iPr)₂)Ir(cod)]; potassium <i>tert</i>-butylate In tetrahydrofuran at 90℃; for 24h; Inert atmosphere;
81%	In diethylene glycol dimethyl ether at 140℃; for 24h;	A generic experiment was as follows. In a two-neck roundbottomflask of 10 mL, 1,2-phenylenediamine (1a, 0.5 mmol),1,2-propyleneglycol (2a, 0.6 mmol), 1.5 mL of diethylene glycol dimethylether (diglyme), and an amount of catalyst were added.Subsequently, the reaction mixture was heated at 140 °C in a siliconebath that contains a magnetic stirrer and a temperature controller.
70%	With C₁₈H₂₄ClIrN₃O⁽¹⁺⁾*Cl^(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry;
69%	With cesiumhydroxide monohydrate; C₁₇H₁₄Br₂CoN₄ In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere;
69%	With potassium hydroxide In toluene at 130℃; for 24h; Inert atmosphere;
65%	With bromopentacarbonylmanganese(I); N,N,N',N'',N'''-pentamethyldiethylenetriamine; potassium <i>tert</i>-butylate In toluene at 130℃; for 36h; Sealed tube; Inert atmosphere; Schlenk technique;

Reference： [1]Daw, Prosenjit; Kumar, Amit; Espinosa-Jalapa, Noel Angel; Diskin-Posner, Yael; Ben-David, Yehoshoa; Milstein, David [ACS Catalysis, 2018, vol. 8, # 9, p. 7734 - 7741]
[2]Panja, Dibyajyoti; Paul, Bhaskar; Balasubramaniam, Bhuvaneshwari; Gupta, Raju K.; Kundu, Sabuj [Catalysis Communications, 2020, vol. 137]
[3]Shee, Sujan; Panja, Dibyajyoti; Kundu, Sabuj [Journal of Organic Chemistry, 2020, vol. 85, # 4, p. 2775 - 2784]
[4]Hille, Toni; Irrgang, Torsten; Kempe, Rhett [Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5569 - 5572]
[5]Location in patent: experimental part Climent; Corma; Hernandez; Hungria; Iborra; Martinez-Silvestre [Journal of Catalysis, 2012, vol. 292, p. 118 - 129]
[6]Chakrabarti, Kaushik; Maji, Milan; Kundu, Sabuj [Green Chemistry, 2019, vol. 21, # 8, p. 1999 - 2004]
[7]Shee, Sujan; Ganguli, Kasturi; Jana, Kalipada; Kundu, Sabuj [Chemical Communications, 2018, vol. 54, # 50, p. 6883 - 6886]
[8]Guo, Bin; Li, Hong-Xi; Zhang, Shi-Qi; Young, David James; Lang, Jian-Ping [ChemCatChem, 2018, vol. 10, # 24, p. 5627 - 5636]
[9]Mondal, Akash; Sahoo, Manoj Kumar; Subaramanian, Murugan; Balaraman, Ekambaram [Journal of Organic Chemistry, 2020, vol. 85, # 11, p. 7181 - 7191]

33
[ 909878-64-4 ]
[ 110-63-4 ]
[ 4435-50-1 ]
[ 18826-95-4 ]
[ 3068-00-6 ]
[ 78-92-2 ]
[ 106-97-8 ]
[ 71-36-3 ]
[ 513-85-9 ]
[ 584-03-2 ]

Reference： [1]ChemSusChem,2012,vol. 5,p. 1991 - 1999

34
[ 3068-00-6 ]
[ 110-63-4 ]
[ 18826-95-4 ]
[ 106-97-8 ]
[ 71-36-3 ]
[ 584-03-2 ]

Reference： [1]ChemSusChem,2012,vol. 5,p. 1991 - 1999

35
trans-1,2-Diaminocyclohexane [ No CAS ]
[ 584-03-2 ]
(2RS,4aSR,8aSR)-2-ethyldecahydroquinoxaline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; sodium hydrogencarbonate In water at 20℃; for 24h; Inert atmosphere; Reflux;	35 Reference Example 35 Production of (2RS,4aSR,8aSR)-2-ethyldecahydroquinoxaline Reference Example 35 Production of (2RS,4aSR,8aSR)-2-ethyldecahydroquinoxaline Relative confi uration Dichloro(pentamethylcyclopentadienyl)iridium (III) dimer (70 mg, 0.090 mmol) and sodium bicarbonate (73 mg, 0.87 mmol) were added to an aqueous (20 mL) solution of trans-cyclohexane-l,2-diamine (2.00 g, 17.5 mmol) and (±)-l,2-butanediol (1.69 mL, 18.4 mmol) with stirring at room temperature. Degassing and argon substitution were repeated 3 times, and the mixture was then stirred for 24 hours under reflux. The reaction mixture was concentrated under reduced pressure. The obtained residue was purified by basic silica gel column chromatography (methylene chloride/methanol) to obtain (2R,4aS,8aS*)-2- ethyldecahydroquinoxaline (2.03 g, yield: 69%) in a yellow solid form. 1H-NMR(CDCl3)5ppm : 0.92 (3H, t, J = 7.5 Hz), 1.10-1.60 (7H, m), 1.64-1.83 (5H, m), 2.16- 2.31 (2H, m), 2.44 (IH, dd, J = 11.5, 10.4 Hz), 2.58-2.67 (1H, m), 3.02 (1H, dd, J = 11.5, 2.7 Hz).

Reference： [1]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - WO2013/137479, 2013, A1 Location in patent: Paragraph 0230

36
[ 584-03-2 ]
[ 5077-67-8 ]
[ 78-93-3 ]
[ 78-92-2 ]

Reference： [1]Chemistry Letters,2014,vol. 43,p. 334 - 336

37
[ 553-90-2 ]
[ 96-35-5 ]
[ 107-21-1 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen In methanol at 219.84℃; Inert atmosphere; Gas phase;	Catalytic activity measurement The catalytic activity test was conducted using a fixed-bed reac-tor. Typically, 0.9 g of catalyst (40-60 meshes) sample are packedinto a stainless steel tubular reactor (i.d. = 5 mm) with a thermocou-ple inserted into the catalyst bed. Catalyst activation was performedat 573 K for 4 h with a ramping rate of 2 K min-1from room tem-perature under the 5% H2/Ar (V/V) atmosphere. After cooling tothe reaction temperature, 10 wt.% DMO (purity > 99%) in methanoland pure H2are fed into the reactor at a H2/DMO molar ratioof 100 and a system pressure of 3.0 MPa. The reaction tempera-tures are set at 493 K and LHSV of DMO is set at the value rangingfrom 0.1 to 1.0 h-1. The products are condensed, and analyzedon a gas chromatograph (Finnigan Trace GC ultra) fitted with anHP-5 capillary column and a flame ionization detector (FID). Theidentification of the products is performed by using a GC-MS spec-trometer. Chromatography is performed on a Thermo Focus DSQgas chromatograph with a mass-selective detector with electronimpact ionization. Analysts are separated using a VF-5MS capillarycolumn of 30 m × 0.25 mm with a phase thickness of 0.25 m from HP, which was inserted directly into the ion source of the MS sys-tem.
	With hydrogen In methanol at 220 - 350℃; for 4h;	4 General procedure: Cu(NO3)2 was formulated with 0.3 mol/L aqueous solution with deionized water, a solution of 157 ml of this solution was placed in a beaker, while stirring slowly add ammonia, the pH of the solution in the beaker was 9.5 to 10.5. weighed 12 g of silica was added to the above-mentioned beaker containing Cu(NO3)2 solution, in the 30 °C water bath stirring aging 4h, heated to 90 °C steamed ammonia, until the beaker solution has a pH of 7 to 8. the resulting precipitate was filtered and washed to a filtrate at a pH of about 7. the washed precipitate was dried at 120 °C for 12 h, 450 ° C calcination 4h, tablet crushing to 20 ~ 40 mesh, pre-reaction reduction to obtain catalyst A: 20 wt% Cu/silica. The above catalyst performance was evaluated in a continuous flowing gas solid phase reactor, The catalyst loading was 1.0g. using a pure hydrogen normal pressure 350 ° C reduction catalyst, flow rate of 100mL/min, the temperature is raised from room temperature to 350 ° C at a rate of 1 to 2 ° C/min, and keep 4h, down to the reaction temperature after the introduction of H2, a 15 wt.% DMO solution of methanol was poured into an advection pump. control the hydrogen ester ratio 150,The system pressure is 2.0 MPa, the reaction temperature was 200 ° C. chromatographic analysis raw materials dimethyl oxalate (DMO) and the product of methyl glycolate (MG), ethylene glycol (EG), ethanol (EO), 2-methoxyethylether (2-MEO), 1,2-propanediol (1,2POD), 1,2-butanediol (1,2BOD).The evaluation results of the catalyst performance are shown in Table 1. The catalyst preparation and evaluation procedure was the same as in Example 1, change the quality of the alleged white silica to 14. 25g, the volume of Cu(NO3)2 solution with a change of the concentration of 3 mol / L was 39. 2 ml, preparation of catalyst Ε: 5 wt% Cu / silica,The evaluation temperature of the reaction was changed to 220 ° C, and the results are shown in Table 1.

Reference： [1]Wen, Chao; Li, Fanqi; Cui, Yuanyuan; Dai, Wei-Lin; Fan, Kangnian [Catalysis Today, 2014, vol. 233, p. 117 - 126]
[2]Current Patent Assignee: Dalian Institute of Chemical Physics (in: CAS); CHINESE ACADEMY OF SCIENCES - CN105622418, 2016, A Location in patent: Paragraph 0020; 0021; 0028; 0029

38
[ 124-38-9 ]
[ 584-03-2 ]
1,2-butylene carbonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With 2-Cyanopyridine; cerium(IV) oxide at 139.84℃; for 1h; Autoclave;
82%	With 1,10-Phenanthroline; calcium carbide; zinc trifluoromethanesulfonate In 1-methyl-pyrrolidin-2-one at 180℃; for 24h; Autoclave; Glovebox; Sealed tube;
40.4%	Stage #1: carbon dioxide With 1-butyl-3-methyl-1H-imidazol-3-iumhydrogencarbonate at 25℃; for 6h; Stage #2: 1,2-dihydroxybutane at 25℃; for 12h;	20 Example 20 In the absorption tank, pass 0.91 kg of carbon dioxide into 4.01 kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate. The absorption tank is kept at a constant temperature of 25°C and stirred for 360 min under normal pressure. The stirring speed is 350 rpm. Absorption obtains a mixture of ionic liquid and carbon dioxide adduct. Introduce the absorption liquid into the reactor, add 1.80kg 1,2-butanediol and 9.98kg diiodomethane (3L, the mass fraction of diiodomethane is 60%), stir and react at 25 and normal pressure for 12h, and the stirring speed is At 600 rpm, the reaction equilibrium is reached.The reaction liquid was analyzed by gas chromatography-mass spectrometer, and it was found that in addition to the volatile reactants, organic carbonate product 1,2-butenyl carbonate was produced; after gas chromatography analysis, the obtained carbonic acid 1,2- -Butene ester selectivity can be as high as 98.3%, and the yield can be as high as 40.4%.

99 %Chromat.	With 1,8-diazabicyclo[5.4.0]undec-7-ene; 2-methyl-but-3-yn-2-ol In N,N-dimethyl-formamide at 120℃; for 10h; Autoclave;	General procedure for the reaction of vicinal diols, propargylic alcohols and CO2 General procedure: The reactions were performed in a 50 ml autoclave with a Teflon vessel inside equipped with magnetic stirring under 3.0 MPa CO2. After introducing DBU (60.8 mg, 0.4 mmol), propylene glycol (76.1 mg, 1 mmol), 2-methyl-3-butyn-2-ol (126.2 mg, 1.5 mmol), DMF (2 ml), the autoclave was sealed and filled with CO2 to keep thepressure of CO2 under 3.0 MPa. Then, the reaction mixture was stirred at 120 °C for 10 h. When the reaction completed, the autoclave was cooled to ambient temperature and residual CO2 was carefully released. Subsequently, the mixture was flushed with DMF and analyzed by GC using biphenyl as an internal standard.
47.6 %Chromat.	With tetraethylammonium iodide In acetonitrile at 20℃; Electrolysis;

Reference： [1]Honda, Masayoshi; Tamura, Masazumi; Nakao, Kenji; Suzuki, Kimihito; Nakagawa, Yoshinao; Tomishige, Keiichi [ACS Catalysis, 2014, vol. 4, # 6, p. 1893 - 1896]
[2]Choi, Jun-Chul; Fujitani, Tadahiro; Fukaya, Norihisa; Lin, Xiao-Tao; Sato, Kazuhiko; Yuan, Hao-Yu; Zhang, Qiao [Green Chemistry, 2020, vol. 22, # 13, p. 4231 - 4239]
[3]Current Patent Assignee: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN111362800, 2020, A Location in patent: Paragraph 0118-0120
[4]Han, Li-Hua; Li, Jing-Yuan; Song, Qing-Wen; Zhang, Kan; Zhang, Qian-Xia; Sun, Xiao-Fang; Liu, Ping [Chinese Chemical Letters, 2020, vol. 31, # 2, p. 341 - 344]
[5]Zhang, Jing-Jie; Li, Shi-Ming; Shi, Yi; Hu, Qiao-Li; Wang, Huan; Lu, Jia-Xing [New Journal of Chemistry, 2020, vol. 44, # 27, p. 11817 - 11823]

39
[ 98-00-0 ]
[ 97-99-4 ]
[ 5343-92-0 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With 5% active carbon-supported ruthenium; hydrogen; In water; at 200℃; under 75007.5 Torr; for 0.75h;Autoclave;	The 6 Ru catalysts and 2 Pt catalysts shown in Table 11 were tested in 100 ml of an aqueous solution of furfuryl alcohol at 200 C. and a hydrogen pressure of 100 bar in a batch reactor. Here, 0.5 g of catalyst and the additives indicated were used in each case. The reaction was stopped as soon as complete conversion of furfuryl alcohol had been achieved. Table 11 summarizes the reaction times for complete conversion and the selectivities to the most important reaction products for the 8 catalysts examined.

Reference： [1]Patent: US2014/243562,2014,A1 .Location in patent: Paragraph 0208

40
[ 584-03-2 ]
[ 5077-67-8 ]
[ 600-15-7 ]

Yield	Reaction Conditions	Operation in experiment
	With 1% platinum on charcoal; oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	Reactions were carried out using a Radley?s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.
45%Spectr.; 55%Spectr.	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.

Reference： [1]Tetrahedron,2014,p. 6055 - 6058
[2]Tetrahedron,2014,vol. 70,p. 6055 - 6058

41
[ 584-03-2 ]
[ 802294-64-0 ]
[ 5077-67-8 ]
[ 600-15-7 ]

Yield	Reaction Conditions	Operation in experiment
	With Au-Pd/carbon catalyst; oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	Reactions were carried out using a Radley?s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.
6%Spectr.; 46%Spectr.; 45%Spectr.	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.

Reference： [1]Tetrahedron,2014,p. 6055 - 6058
[2]Tetrahedron,2014,vol. 70,p. 6055 - 6058

42
[ 584-03-2 ]
[ 64-19-7 ]
[ 802294-64-0 ]
[ 5077-67-8 ]
[ 600-15-7 ]

Yield	Reaction Conditions	Operation in experiment
	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	Reactions were carried out using a Radley?s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.
7%Spectr.; 11%Spectr.; 28%Spectr.; 54%Spectr.	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.
7%Spectr.; 11%Spectr.; 28%Spectr.; 54%Spectr.	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.

Reference： [1]Tetrahedron,2014,p. 6055 - 6058
[2]Tetrahedron,2014,vol. 70,p. 6055 - 6058
[3]Tetrahedron,2014,vol. 70,p. 6055 - 6058

43
[ 584-03-2 ]
[ 64-19-7 ]
[ 5077-67-8 ]
[ 600-15-7 ]

Yield	Reaction Conditions	Operation in experiment
	With oxygen; In water; at 100℃; under 2250.23 Torr; for 24h;	Reactions were carried out using a Radley?s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104percent. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support.

Reference： [1]Tetrahedron,2014,p. 6055 - 6058

44
[ 9004-34-6 ]
[ 57-55-6 ]
[ 107-21-1 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 50% 2: 7.4% 3: 6.7%	With Rh/C; hydrogen; ortho-tungstic acid; copper(II) sulfate In water at 245℃; for 0.5h; Autoclave;	2.2. Reaction General procedure: The reaction of cellulose conversion to glycolaldehyde was con-ducted in a ∼16.7 mL batch reactor (length of 200 mm, OD of 16 mm,ID of 10 mm, Stainless steel 904L) equipped with a pressure gauge and a relief valve. This reactor system could cover a range in pres-sure and temperature up to 30 MPa and 400°C, respectively. In a typical procedure, cellulose (0.1 g), a designated amount of cata-lyst, and water (10 mL) were put into the reactor which was then sealed. After that, the reactor was quickly heated by immersing it into the molten tin bath with a preset reaction temperature. After the desired reaction time, the reaction vessel was quickly move dinto an ice-water bath to stop the reaction. The real reaction time was calculated by subtracting the heating time (about 30 s) from the whole immersion time.The reaction of cellulose conversion to ethylene glycol wasconducted in a 75 mL stainless steel autoclave (Parr InstrumentCompany) typically at 6MPa H2 pressure (measured at room tem-perature) and 245°C for 30 min. For each reaction, 0.25 g cellulose,0.075 g Ru/C, 0.0125 g H2WO4 and 25 mL water were put into there actor, and stirred at rate of 800 rpm.
1: 23.2% 2: 12.8% 3: 6%	With phosphotungstic acid; platinum on activated charcoal; hydrogen In water at 250℃; for 0.833333h; Autoclave;
	With hydrogen In water at 219.84℃; for 8h; Autoclave;

Reference： [1]Xu, Gang; Wang, Aiqin; Pang, Jifeng; Zheng, Mingyuan; Yin, Jianzhong; Zhang, Tao [Applied Catalysis A: General, 2015, vol. 502, p. 65 - 70]
[2]Zhang, Kai; Wu, Shubin; Yang, He; Yin, Huimin; Li, Gang [RSC Advances, 2016, vol. 6, # 81, p. 77499 - 77506]
[3]Lucas, Martin; Fabičovicová, Katarina; Claus, Peter [ChemCatChem, 2018, vol. 10, # 3, p. 612 - 618]

45
[ 50-99-7 ]
[ 57-55-6 ]
[ 107-21-1 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 33.3% 2: 7.6% 3: 7.1%	With palladium on activated charcoal; water; zinc at 250℃; for 0.5h;
	With 5% active carbon-supported ruthenium; hydrogen; ortho-tungstic acid; sodium hydroxide In water; glycerol at 200℃; for 4h;	2 A CSTR provided with a stirrer and having a volume of 3.5 ml was filled with 100 mg of a hydrogenolysis catalyst comprising 5%wt ruthenium on active carbon. A feedstock comprising 5%wt glucose in a mixture of water and glycerol (82%wt water and 18%wt glycerol), based on the weight of the mixture, was fed into the CSTR. The feedstock further comprised 0.8 g sodium hydroxide per liter of the mixture. The feedstock flow also contained 1 %wt tungstic acid (H2W04). The reaction temperature was kept at 200 °C, the hydrogen pressure was 50 bar, and the stirrer speed was 1000 rpm. The weight ratio of tungsten to ruthenium in the experiment was 2.2 wt/wt. The weight ratio of ruthenium to glucose introduced into the CSTR was 1 : 115. The flow of liquid feedstock was 0.15 ml/min, and the hydrogen flow was 100 ml/min. The residence time of the liquid in the reactor was therefore about 23.3 min. It appeared that the conversion of glucose was constant at about 98.5%. The effluent was analyzed and the selectivities towards ethylene glycol (sEG), propylene glycol (sPG) and butylene glycol (sBG) were determined. The selectivities were calculated as the amounts of ethylene glycol, propylene glycol and butylene glycol were determined, calculated as the weight percentage in the reactor effluent divided by the amount of grams glucose being introduced into the CSTR.

Reference： [1]Wang, Jie; Yao, Guodong; Wang, Yuanqing; Zhang, Hua; Huo, Zhibao; Jin, Fangming [RSC Advances, 2015, vol. 5, # 63, p. 51435 - 51439]
[2]Current Patent Assignee: AVANTIUM N.V. - WO2016/114661, 2016, A1 Location in patent: Page/Page column 14-15

46
[ 109-65-9 ]
[ 124-38-9 ]
[ 584-03-2 ]
1,2-butylene carbonate [ No CAS ]
[ 542-52-9 ]

Yield	Reaction Conditions	Operation in experiment
96 %Spectr.	Stage #1: carbon dioxide; 1,2-dihydroxybutane With 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,2-dichloro-ethane at 25℃; Stage #2: 1-bromo-butane In 1,2-dichloro-ethane at 25℃; for 24h;	General procedure for the synthesis of cyclic carbonates 2 General procedure: Compound 1 (2.5 mmol) and DBU (20 mmol) in DCE (1mL) were placed in a 50-mL two-necked flask and CO2 gas was flowed with stirring at 25 °C until the solution was changed to a white suspension. After addition of 1-bromobutane (24 mmol), the flask was capped with a rubber septum and equipped with a CO2 balloon. The mixture was stirred at 25 °C for 24 h and then passed through a short pad of silica gel with CH2Cl2 as eluent to remove the DBU salts. The eluent was concentrated under reduced pressure and the yield of the product was determined by 1H NMR using an internal standard. The product 2 was separated by column chromatography on silica gel using hexane and/or CH2Cl2 as eluent.

Reference： [1]Kitamura, Tsugio; Inoue, Yusuke; Maeda, Taisei; Oyamada, Juzo [Synthetic Communications, 2016, vol. 46, # 1, p. 39 - 45]

47
[ 492-62-6 ]
[ 57-55-6 ]
[ 50-70-4 ]
[ 107-21-1 ]
[ 56-81-5 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen In water at 180℃;	Catalytic reaction process General procedure: Hydrogenolysis of glucose was performed in a vertical fixed-bed reactor (i.d. 12 mm, length 600 mm) with a cold trap. Prior to the test, 2.0 g catalyst (20-40 mesh) was loaded at the isothermal zone and in situ reduced at 250 °C for 2 h in hydrogen (100 mL/min). After reduction, a 5 wt% aqueous glucose solution was pumped into the reactor, and mixed with H2 co-feeding. The liquid products were collected in a gas-liquid separator immersed in an ice-water trap. Typical reaction conditions were as follows: 4 MPa H2 (45 mL/min), 5 wt% aqueous glucose solution, aqueous glucose solution flow rates were set as 24, 19.2, and 14.4 mL/h, which can be shown as 0.6, 0.48, and 0.36 h-1 in WHSV (weight hourly space velocity).

Reference： [1]Liu, Chengwei; Zhang, Chenghua; Zhu, Yulei; Li, Yongwang; Hao, Shunli; Sun, Sikai; Liu, Kangkai; Xu, Jian [Catalysis Today, 2016, vol. 261, p. 116 - 127]

48
[ 616-38-6 ]
[ 584-03-2 ]
1,2-butylene carbonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	In neat (no solvent) at 110℃; for 24h; Green chemistry;
	With zinc(II) trifluoroacetate hydrate; 1,3-bis(imidazol-1-ylmethyl)benzene for 9h; Reflux;	31 Example 31 Cyclic Carbonate Formation Reactions ( Example 31 Cyclic Carbonate Formation Reactions (0197) In a dimethyl carbonate solvent, 1,2-butanediol was refluxed for 5 hours with the zinc catalyst A (a catalyst ratio of 2 mol %) being used. The conversion of 1,2-butanediol to 4-ethyl-1,3-dioxolan-2-one was 94%. In addition, another reaction was conducted by adding zinc trifluoroacetate hydrate (a catalyst ratio of 2 mol %) and the ligand (A) (a catalyst ratio of 4 mol %) in the same manner. Consequently, the raw material 1,2-butanediol disappeared in 9 hours, and the cyclic carbonate was successfully obtained as in the case where the zinc catalyst A was used.
	With tetrabutylammomium bromide at 180℃; for 0.05h; Flow reactor;

With sodium methylate In methanol at 64 - 90℃;

1 Synthesis of 1,2-butylene carbonate Ina 300 mL reactor equipped with a stirrer, thermometer, gas introduction tube, and cooling tube, 50 g (0.56 mol) of 1,2-butanediol and 55.0 g of dimethyl carbonate (0.61 mol), 1.07 g (0.0056 mol) of 28% sodium methoxide (methanol solution) was charged, reacted at 64 ° C. for 3 hours, and then raised to 90 ° C. while removing the produced methanol. It was warm.Then, the target product was distilled and purified under reduced pressure to obtain the desired 1,2-butylene carbonate as a liquid product.

Reference： [1]Pyo, Sang-Hyun; Hatti-Kaul, Rajni [Advanced Synthesis and Catalysis, 2016, vol. 358, # 5, p. 834 - 839]
[2]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2016/2268, 2016, A1 Location in patent: Paragraph 0197
[3]Gérardy, Romaric; Estager, Julien; Luis, Patricia; Debecker, Damien P.; Monbaliu, Jean-Christophe M. [Catalysis science and technology, 2019, vol. 9, # 24, p. 6841 - 6851]
[4]Current Patent Assignee: NIPPON FINE CHEMICAL CO LTD - JP2020/158397, 2020, A Location in patent: Paragraph 0041

49
[ 59765-97-8 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
98.5%	With water Reflux;	2 Example 2 Using the flow shown in Figure 1,1,2-butanediol acetal compound(4-ethyl-2-methyl-1,3-dioxolane) with water from 9thBlock theoretical plate into the hydrolysis distillation column,The molar ratio of water to acetal compound was 1.6: 1,The total theoretical plate number of the hydrolysis distillation column is 19,Paragraph 7 ~ 14 set the reaction section,Atmospheric pressure operation,Reflux ratio of 0.4,The top of the tower controls the purity of acetaldehyde,Tower kettle control acetal content,The kettle takes out the mixture of 1,2-butanediol and water into the middle part of the butanediol refining tower;Butanediol refined the total number of theoretical plate 8,The operating pressure was 0.1 atm in absolute pressure,Reflux ratio of 0.1,The tower kettle controls the purity of butanediol.After the above process,1,2-butanediol product quality and easy to reach 99.0% purity,The yield of 1,2-butanediol was 98.5%.

Reference： [1]Current Patent Assignee: TIANJIN UNIVERSITY - CN105693466, 2016, A Location in patent: Paragraph 0036; 0037

50
[ 50-70-4 ]
[ 57-55-6 ]
[ 34557-54-5 ]
[ 64-17-5 ]
[ 5343-92-0 ]
[ 6920-22-5 ]
[ 909878-64-4 ]
[ 69-65-8 ]
[ 584-02-1 ]
[ 124-38-9 ]
[ 107-21-1 ]
[ 56-81-5 ]
[ 78-92-2 ]
[ 504-63-2 ]
[ 513-85-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen; sodium hydroxide; In water; at 210℃; under 45004.5 Torr; for 2h;Autoclave;	General procedure: The hydrogenolysis of sorbitol was performed in a 50 mL stainless-steel autoclave with magnetic stirring. After sorbitol aqueous solution, Ru catalyst and an appropriate amount of basewere charged into the reactor, the autoclave was purged with hydrogen four times and then pressurized to the desired pressure at room temperature. Then the reaction was performed atcertain temperature under the stirring speed of 800 r/min. After the reaction, the reactor was cooled down and the used catalystwas separated from the reaction mixture by centrifugation. Thesamples were filtered through 0.22 m-pore-size filters (Mem-brana) prior to analysis. The obtained products such as 1,2-PG,EG and GLY were determined using a gas chromatography (GC,7890A, Agilent, USA) equipped with a CP-Wax 58 (FFAP) capillarycolumn (0.25 mm × 25 m) and a flame ionization detector. Otherproducts like glucose, sugar alcohols were quantified by Anion-Exchange Chromatography (IC, Dionex ICS-3000) equipped with pulsed amperometric detector and an Aminex HPX-87H column(Bio-Rad, 7.8 × 300 mm), using 500 mM NaOH as eluent with a flowrate of 0.4 mL min-1at 30C. The obtained products in resultant solutions were also identified by GC-MS (6890N, Agilent, USA). The conversion of sorbitol and yields of products were calculated on the carbon basis and defined as follows

Reference： [1]Journal of Molecular Catalysis A: Chemical,2017,vol. 426,p. 79 - 87

51
[ 50-70-4 ]
[ 57-55-6 ]
[ 34557-54-5 ]
[ 64-17-5 ]
[ 5343-92-0 ]
[ 6920-22-5 ]
[ 909878-64-4 ]
[ 69-65-8 ]
[ 584-02-1 ]
[ 124-38-9 ]
[ 107-21-1 ]
[ 56-81-5 ]
[ 78-92-2 ]
[ 513-85-9 ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen; sodium hydroxide; at 210℃; under 45004.5 Torr; for 2h;	General procedure: The hydrogenolysis of sorbitol was performed in a 50 mL stainless-steel autoclave with magnetic stirring. After sorbitol aqueous solution, Ru catalyst and an appropriate amount of basewere charged into the reactor, the autoclave was purged with hydrogen four times and then pressurized to the desired pressure at room temperature. Then the reaction was performed atcertain temperature under the stirring speed of 800 r/min. After the reaction, the reactor was cooled down and the used catalystwas separated from the reaction mixture by centrifugation. Thesamples were filtered through 0.22 m-pore-size filters (Mem-brana) prior to analysis. The obtained products such as 1,2-PG,EG and GLY were determined using a gas chromatography (GC,7890A, Agilent, USA) equipped with a CP-Wax 58 (FFAP) capillarycolumn (0.25 mm × 25 m) and a flame ionization detector. Otherproducts like glucose, sugar alcohols were quantified by Anion-Exchange Chromatography (IC, Dionex ICS-3000) equipped with pulsed amperometric detector and an Aminex HPX-87H column(Bio-Rad, 7.8 × 300 mm), using 500 mM NaOH as eluent with a flowrate of 0.4 mL min-1at 30C. The obtained products in resultant solutions were also identified by GC-MS (6890N, Agilent, USA). The conversion of sorbitol and yields of products were calculated on the carbon basis and defined as follows

Reference： [1]Journal of Molecular Catalysis A: Chemical,2017,vol. 426,p. 79 - 87

52
[ 111-27-3 ]
[ 584-03-2 ]
C₁₆H₃₆O₆P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88.3%	With pyridine; phosphorus trichloride In chloroform at 10℃; for 2h;	4 Example 4 In a vacuum system with mechanical agitation, a thermometer, an inlet conduit and an HCl absorber connected, 55.3 g of phosphorus trichloride and 40.0 g of chloroform, and 10.0 g of pyridine were added,Should be placed in the cold bath at 10 , stirring mixing, open the vacuum pump to control the reaction system pressure15 to 20 KPa. When the temperature of the reactant drops to 0 ° C, a solution of 84.3 g of n-hexanol and 18.4 g of 1,2-Alcohol mixture of alcohol. The HCl generated by the synthesis reaction was mainly withdrawn from the vacuum pump,Sodium hydroxide solution absorption, a small amount of HCl is not discharged by the acid binding agent absorption reaction.The dropping rate was controlled, the mixed alcohol was dripped in 60 min, and the reaction was stopped for 60 min. After completion of the reaction,The solvent and the by-products were removed by distillation under reduced pressure. When the pressure was in the range of 0.01 to 0.02 kPa, the distillation was carried out at 140 to 145C(Mono-n-hexyl-phosphite) -1,2-butanediol, and the distillate fractions of bis (monophosphoric acid mono-n-hexanolEster) -l, 2-butanediol was 96.6%. The yield of bis (n-hexyl-phosphite) -l, 2-butanediol was88.3%.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN104177406, 2016, B Location in patent: Paragraph 0039; 0040; 0041

53
[ 71-36-3 ]
[ 584-03-2 ]
C₁₂H₂₈O₆P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87.1%	With pyridine; phosphorus trichloride at 0℃; for 1.5h;	3 Example 3 in a reaction vessel equipped with a mechanical stirrer, a thermometer, an inlet duct and an evacuation system connected to the HC1 absorber, 55.3 g of phosphorus trichloride and 30. Og of 1-chlorobutane, and 10. Og of pyridine were added and the reaction vessel was cooled at 0 ° CBath, mixing, open the vacuum chestnut, control reaction system pressure of 15 ~ 20KPa, when the reactant temperature dropped to 0 ° C, the dropAnd a mixed alcohol obtained by mixing 61.2 g of n-butanol and 18.4 g of 1,2-butanediol. HC1 produced by the synthesis reaction is mainly composed of trueEmpty chestnut out, and by three 40% sodium hydroxide solution absorption, a small amount of HC1 is not discharged by acid binding agent absorption reaction.[0038] The dropping rate was controlled and the mixed alcohol was dropped over 40 min and the reaction was stopped for 50 min. After completion of the reaction, the reaction mixture was distilled under reduced pressureRemoval of solvents and by-products, at a pressure of 0.05 ~ 0.08KPa, the collection of 128 ~ 133 ° C fractions obtained two (single phosphorous acidButanediol) -l, 2-butanediol, the content of bis (n-butyl phosphite) -l, 2-butanediol in the collected fraction was97.9%. The yield of bis (mono-n-butyl phosphite) -1,2-butanediol was 87.1%.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN104177406, 2016, B Location in patent: Paragraph 0036; 0037; 0038

54
[ 9004-34-6 ]
[ 57-55-6 ]
[ 149-32-6 ]
[ 107-21-1 ]
[ 584-03-2 ]

Reference： [1]RSC Advances,2017,vol. 7,p. 8567 - 8574

55
[ 50-70-4 ]
[ 106-69-4 ]
[ 140946-33-4 ]
1,2,5,6-hexanetetrol [ No CAS ]
[ 584-03-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 46.12% 2: 26.54% 3: 5.51% 4: 10.26%	With propylene glycol; hydrogen; copper In water at 210℃;	10 Example 10 Preparation of 1,2,5,6-Hexanetetrol from Sorbitol in Water/Propylene Glycol with Raney Copper Solutions containing 25% wt/wt sorbitol, about 25% wt/wt water and about 50% weight propylene glycol as shown in Table 3 were passed through a Raney copper fixed bed reactor system as described in Examples 8 and 9, at 210° C. and a pressure of 1800 psi. The resulting reaction mixture was analyzed for propylene glycol (PG), ethylene glycol (EG) 1,2 hexanediol (1,2-HDO), 1,2 butanediol (1,2-BDO), 1,2,6 hexanetriol, (1,3,6-HTO), 1,4,5 hexanetriol (1,4,5-HTO) and 1,2,5,6 hexanetetrol (1,2,5,6-ITO) with the results shown in Table 4.

Reference： [1]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - US2017/121258, 2017, A1 Location in patent: Paragraph 0070

56
p-methoxy-benzyl 2,7-dimethyl pixyl ether [ No CAS ]
[ 584-03-2 ]
C₂₅H₂₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 1.5h; Molecular sieve; Inert atmosphere; regiospecific reaction;	Common experimental procedure for DMPx protection General procedure: To a mixture of alcohol (1.0 mmol) and p-methoxy benzoyl-pixyl ether l (MBDPE) (1.2mmol) activated molecular sieves 4Å (0.3 g) in anhydrous dichloromethane (5 ml) undernitrogen was added DDQ (1.5 mmol) and the reaction mixture was stirred at roomtemperature for given time (Table 1 and 2). After completion of the starting material(monitored by TLC), the reaction mixture was quenched with sat. NaHCO3 (5 ml). Thelayers were separated and the aqueous layer is extracted with dichloromethane (2 x 5 ml)and the combined organic layers were washed with water (2 x 5 ml) and brine (1 x 5 ml).The organic layer was dried over anhydrous Na2SO4 and evaporated under vacuum. Theobrained crude compound was purified by silica gel column chromatography to affordthe DMPx ether in good to excellent yields.

Reference： [1]Srishylam, Penjarla; Raji Reddy; Banerjee, Shyamapada; Penta, Santhosh; Sanghvi, Yogesh S. [Tetrahedron Letters, 2017, vol. 58, # 26, p. 2588 - 2591]

57
[ 107-15-3 ]
[ 584-03-2 ]
[ 13961-37-0 ]

Yield	Reaction Conditions	Operation in experiment
64.1%	With hydrogen; magnesium sulfate at 180℃; for 6h; Autoclave;	3 Example 3 Synthesis of 2-ethylpiperazine from ethylenediamine and 1,2-butanediol. 30 g (0.50 mol) of ethylenediamine, 90 g (1.0 mol) of 1,2-butanediol and Raney copper (trade name: CDT-60, manufactured by Kawaken Fine Chemicals Co., Ltd.) as a catalyst were charged into an autoclave having an internal volume of 200 ml. , And 10.0 g of anhydrous magnesium sulfate as a dehydrating agent, and the mixture was heated to 180 ° C. in a hydrogen atmosphere. The pressure of the reaction vessel at this time was 4.5 MPa.Reacted for 6 hours,Analysis of the product by gas chromatography revealed that the conversion of ethylenediamine was 76.2%The yield of 2,3-dimethylpiperazine was 64.1%, and the selectivity was 84.8%.

Reference： [1]Current Patent Assignee: TOSOH CORPORATION - JP5803619, 2015, B2 Location in patent: Paragraph 0066

58
[ 909878-64-4 ]
[ 109-99-9 ]
[ 453-20-3 ]
[ 110-63-4 ]
[ 4435-50-1 ]
[ 18826-95-4 ]
[ 3068-00-6 ]
[ 6968-16-7 ]
[ 4358-64-9 ]
[ 513-85-9 ]
[ 584-03-2 ]