4-Methylbenzenesulfonohydrazide (TsNHNH2) [C7H10N2O2S]

4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Query Query

Results

Date

11 reactions in Reaxys

2018-08-12 14h:02m:08s (UTC)

O O

1. Query H 2N

S NH

Search as: Product, As drawn, No mixtures ) AND (IDE.RN='1576-35-8') AND (IDE.INCHI='ICGLPKIVTVWCFTUHFFFAOYSA-N') NOT (RX.RXRN=610130))

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

O O

H 2N

S

NH O

Cl

S O

Rx-ID: 733994 View in Reaxys 1/11 Yield 92 %

Conditions & References Typical procedure for preparation of aryl sulfonohydrazides. Preparation Method II (see Scheme 3) General procedure: Preparation of 4-nitrobenzenesulfonohydrazide (H5). A water (300ml) solution of hydrazine hydrate (12.5g; 0.25mol) was cooled in ice-water bath to ∼5°C. The temperature was then maintained below 8°C, while the tetrahydrofuran (50ml) solution of 4-nitrobenzenesulfonyl chloride (5.54g, 0.025mol) was slowly added with stirring. After the addition was completed the reaction mixture was stirred at room temperature for thirty minutes and tetrahydrofuran was evaporated at reduced pressure. The white solid product was separated by filtration, washed with water (3×15ml) and dried on air overnight to give pure product (4.86g; 89percent).

With hydrazine hydrate in tetrahydrofuran, water, T= 0 - 20 °C Backes, Gregory L.; Neumann, Donna M.; Jursic, Branko S.; Bioorganic and Medicinal Chemistry; vol. 22; nb. 17; (2014); p. 4629 - 4636 View in Reaxys

92 %

Preparation of 4-methoxybenzenesulfonohydrazide(SH3).

General procedure: A water (300 ml) solution of hydrazine hydrate(12.5 g; 0.25 mol) was cooled in an ice-water bath to 5 C. Atetrahydrofuran (50 ml) solution containing 4-methoxybenzenesulfonylchloride (5.16 g, 0.025 mol) was slowly added while stirringslowly. Following this addition, the reaction mixture wasstirred at 5 C for an additional 30 min, and then the tetrahydrofuranwas evaporated at reduced pressure and room temperature.

With hydrazine hydrate in tetrahydrofuran, water, T= 5 °C Backes, Gregory L.; Jursic, Branko S.; Neumann, Donna M.; Bioorganic and Medicinal Chemistry; vol. 23; nb. 13; (2015); p. 3397 - 3407; Art.No: 12252 View in Reaxys

90 %

With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C Zhang, Datong; Ma, Yuntong; Liu, Yu; Liu, Zhao-Peng; Archiv der Pharmazie; vol. 347; nb. 8; (2014); p. 576 - 588 View in Reaxys

86.7 %

2.A :A, in a 100ml round-bottomed flask followed by 1.02g (5.3mmol) of p-toluenesulfonyl chloride, 15mL of toluene, stirred and dissolved to give a solution X, at 15 ° C slowly added dropwise 1.7mL (12mmol) of 80percent hydrazine hydrate to the solution X, drip finished within 5min; continue the reaction 30min, the flask appeared white precipitate.TLC analysis to determine the end of the reaction.After the reaction was completed, 30 ml of water at 10 ° C was added and the mixture was stirred and suction filtered. The filter cake was washed with purified water for 3-5 times and dried to obtain 0.93 g of white p-toluenesulfonyl hydrazide crystals in 86.7percent yield (literature value: yield 92percent).

With hydrazine hydrate in toluene, Time= 0.5h, T= 15 °C , Concentration Patent; Li Jianheng; Ma Siyue; (7 pag.); CN107056871; (2017); (A) Chinese View in Reaxys

83 %

2.2.2. General procedure for the synthesis of arylsulfonyl hydrazides(3 and 4) General procedure: Hydrazine mono hydrate (1.40 mL, 15 mmol) was slowly addedto a 10e15 C cooled and stirred solution of appropriate arylsulfonylchloride (10 mmol) in THF (10 mL). After complete addition,the resulting mixturewas stirred for 15 min. in ice bath maintainingthe same low temperature. Clear one spot for the product on TLCindicated the completion of reaction. Cold water (100 mL) wasadded to the reaction mixture, which precipitated out the product.Precipitates were filtered, washed with cold water and dried in air.Sulfonylhydrazides 3 or 4 were obtained as pure white solid.

With hydrazine hydrate in tetrahydrofuran, Time= 0.25h, T= 10 - 15 °C Arshad, Muhammad; Jadoon, Mehwish; Iqbal, Zafar; Fatima, Mehwish; Ali, Muhammad; Ayub, Khurshid; Qureshi, Ashfaq Mahmood; Ashraf, Muhammad; Arshad, Muhammad Nadeem; Asiri, Abdullah M.; Waseem, Amir; Mahmood, Tariq; Journal of Molecular Structure; vol. 1133; (2017); p. 80 - 89 View in Reaxys

74 %

With hydrazine hydrate in tetrahydrofuran, T= 5 °C

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Fernandes, Thais B.; Cunha, Micael R.; Sakata, Renata P.; Candido, Thalita M.; Baby, André R.; Tavares, Maurício T.; Barbosa, Euzébio G.; Almeida, Wanda P.; Parise-Filho, Roberto; Archiv der Pharmazie; vol. 350; nb. 11; (2017); Art.No: 1700163 View in Reaxys 67 %

9 : p-Toluenesulfonylhydrazide (9) A solution of p-toluenesulfonyl chloride (4.7 g, 25 mmol) in benzene or toluene (100 mL) and 50percent aq hydrazine (5 g, 50 mmol) was magnetically stirred until solidification (ca. 10 min), and the mixture was left for 3 h. The colorless solid material was filtered, washed with ice-cold water, and crystallized from hot water to yield 9 (3.1 g, 67percent); mp 109–111 °C; lit.31 mp 112 °C. 1H NMR (DMSO-d6): 8.31 (s, 1H, exchangeable), 7.70 (d, J = 8.1 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 4.06 (bs, 2H, exchangeable), 2.39 (s, 3H). 13C NMR (DMOS-d6): 142.9. 135.2, 129.5, 127.7, 21.0.

With hydrazine in water, benzene, Time= 3.16667h, Solvent Da Paixao Soares, Fabio; Silva, Maria Joselice E; Doboszewski, Bogdan; Carbohydrate Research; vol. 380; (2013); p. 143 148 View in Reaxys

65 %

With hydrazine hydrate in benzene, Time= 2h, T= 60 - 70 °C Liu, Fei; Yang, Jin-Feng; Liu, Hong; Wei, Wen-Zhen; Ma, Yan-Mei; Journal of the Chinese Chemical Society; vol. 63; nb. 3; (2016); p. 254 - 260 View in Reaxys

39 %

With hydrazine hydrate in water, Time= 2h, T= 0 °C , Inert atmosphere Tripathi, Chandra Bhushan; Mukherjee, Santanu; Organic Letters; vol. 16; nb. 12; (2014); p. 3368 - 3371 View in Reaxys With ethanol, hydrazine hydrate Borsche; Frank; Justus Liebigs Annalen der Chemie; vol. 450; (1926); p. 79 View in Reaxys With tetrahydrofuran, water, hydrazine Friedman; Litle; Reichle; Organic Syntheses; vol. 40; (1960); p. 93 View in Reaxys With hydrazine hydrate Grekov, A. P.; Savel'ev, Yu. V.; Veselov, V. Ya.; Journal of Organic Chemistry USSR (English Translation); vol. 21; nb. 12; (1985); p. 2324 - 2331; Zhurnal Organicheskoi Khimii; vol. 21; nb. 12; (1985); p. 2542 - 2549 View in Reaxys Kumar; Singh; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 40; nb. 7; (2001); p. 579 - 583 View in Reaxys With hydrazine hydrate in water, toluene, Time= 15h, Ambient temperature Bartmann; Synthesis; nb. 5; (1993); p. 490 - 496 View in Reaxys With potassium carbonate, hydrazine in tetrahydrofuran, water, Time= 5h, Ambient temperature Briganti; Pierattelli; Scozzafava; Supuran; European Journal of Medicinal Chemistry; vol. 31; nb. 12; (1996); p. 1001 - 1010 View in Reaxys With hydrazine hydrate, Substitution Dolgopalets; Volkov; Kisel'; Kozhevko; Kulinkovich; Russian Journal of Organic Chemistry; vol. 35; nb. 10; (1999); p. 1436 1438 View in Reaxys With hydrazine in dichloromethane, Time= 0.25h Siemann, Stefan; Evanoff, Darryl P.; Marrone, Laura; Clarke, Anthony J.; Viswanatha, Thammaiah; Dmitrienko, Gary I.; Antimicrobial Agents and Chemotherapy; vol. 46; nb. 8; (2002); p. 2450 - 2457

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

View in Reaxys 1 : EXAMPLE 1: EXAMPLE 1: p-Toluenesulfonohydrazide A solution of 95 g of paratoluenesulfonyl chloride in 170 ml of THF is cooled to 4° C. A solution of hydrazine hydrate is then added dropwise, the temperature being kept at between 10° and 15° C. The mixture is allowed to return to room temperature and decanted and the organic phase is washed twice with a saturated aqueous solution of NaCl and dried.

It is taken up with an equivalent volume of petroleum ether to give a white precipitate of p-toluenesulfonohydrazide.

Melting point: 110° C. With hydrazine hydrate, sodium chloride in tetrahydrofuran Patent; Laboratories UPSA; US5219839; (1993); (A) English View in Reaxys 6 : EXAMPLE 6 EXAMPLE 6 In a similar manner to that described in Example 3, the following compounds are prepared: p-Toluenesulfonic acid 2-[(3-amino-5,6-dichloropyrazinyl)methylene]hydrazide by the reaction of p-toluenesulfonyl chloride with hydrazine in tetrahydrofuran to form p-toluenesulfonylhydrazine, followed by the reaction of the latter with 3-amino-5,6dichloropyrazinaldehyde.

With hydrazine in tetrahydrofuran Patent; Merck and Co., Inc.; US4479953; (1984); (A) English View in Reaxys With hydrazine Phillips, Oludotun A.; Udo, Edet E.; Abdel-Hamid, Mohammed E.; Varghese, Reny; European Journal of Medicinal Chemistry; vol. 44; nb. 8; (2009); p. 3217 - 3227 View in Reaxys With hydrazine hydrate in ethanol, water, Time= 5h, T= 20 °C Tian, Baohe; He, Meizi; Tang, Shixing; Hewlett, Indira; Tan, Zhiwu; Li, Jiebo; Jin, Yinxue; Yang, Ming; Bioorganic and Medicinal Chemistry Letters; vol. 19; nb. 8; (2009); p. 2162 - 2167 View in Reaxys With hydrazine hydrate in tetrahydrofuran Campos, Vinicius R.; Abreu, Paula A.; Castro, Helena C.; Rodrigues, Carlos R.; Jordao, Alessandro K.; Ferreira, Vitor F.; De Souza, Maria C. B. V.; Santos, Fernanda Da C.; Moura, Laura-A.; Domingos, Thaisa S.; Carvalho, Carla; Sanchez, Eladio F.; Fuly, Andre L.; Cunha, Anna C.; Bioorganic and Medicinal Chemistry; vol. 17; nb. 21; (2009); p. 7429 7434 View in Reaxys With hydrazine hydrate in water, T= 0 - 20 °C Wu, Peng; Su, Yi; Liu, Xiaowen; Zhang, Lei; Ye, Yong; Xu, Jianchao; Weng, Shaoyu; Li, Yani; Liu, Tao; Huang, Shufang; Yang, Bo; He, Qiaojun; Hu, Yongzhou; European Journal of Medicinal Chemistry; vol. 46; nb. 11; (2011); p. 5540 5548 View in Reaxys Wu, Peng; Su, Yi; Liu, Xiaowen; Yang, Bo; He, Qiaojun; Hu, Yongzhou; Bioorganic and Medicinal Chemistry; vol. 20; nb.

9; (2012); p. 2837 - 2844 View in Reaxys With hydrazine hydrate in water, Time= 5h, T= 5 - 20 °C Chen, Hua; Yang, Jinliang; Guo, Dongfang; Wang, Liyuan; Nie, Jun; Journal of Photochemistry and Photobiology A: Chemistry; vol. 232; (2012); p. 57 - 63 View in Reaxys With hydrazine hydrate in water, T= 0 - 20 °C

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Wu, Peng; Su, Yi; Liu, Xiaowen; Yang, Bo; He, Qiaojun; Hu, Yongzhou; Bioorganic and Medicinal Chemistry; vol. 20; nb.

9; (2012); p. 2837 - 2844 View in Reaxys With water, hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Yu, Xinzhang; Li, Xingwei; Wan, Boshun; Organic and Biomolecular Chemistry; vol. 10; nb. 37; (2012); p. 7479 - 7482 View in Reaxys With sodium hydroxide, hydrazinium sulfate in water, T= 20 - 90 °C , pH= 7.3 Mamedov; Mamedova; Guseinov; Ladokhina; Fatalizade; Farzaliev; Petroleum Chemistry; vol. 52; nb. 4; (2012); p. 284 287 View in Reaxys 4.4. General procedure for the preparation of arylsulfonylhydrazides (11t-v) General procedure: To a stirred solution of appropriate sulfonyl chloride (0.0025 mol) in dichloromethane (5 mL), a solution of anhydrous hydrazine (0.0125 mol) was added for 2 min and stirred for 15 min and its pH was adjusted to about 11 by adding 10percent Na2CO3 solution. The layers were separated and the aqueous phase was extracted with dichloromethane (25 mL x 3).

The combined organic layers were dried over MgSO4, filtered and the solvent was removed under a reduced pressure at which no further purification of the product was necessary. In case of 11v, the product obtained in step-1 i.e., 11u was hydrolyzed in the presence of 40percent NaOH to obtain 11v as a white crystalline powder.

With sodium carbonate, hydrazine in dichloromethane, Time= 0.283333h, pH= 11 More, Uttam A.; Joshi, Shrinivas D.; Aminabhavi, Tejraj M.; Gadad, Andanappa K.; Nadagouda, Mallikarjuna N.; Kulkarni, Venkatrao H.; European Journal of Medicinal Chemistry; vol. 71; (2014); p. 199 - 218 View in Reaxys With hydrazine hydrate in ethanol Singh; Rawat, Poonam; Kumar, Amit; Journal of Molecular Structure; vol. 1061; nb. 1; (2014); p. 140 - 149 View in Reaxys With hydrazine in tetrahydrofuran, water, T= 0 °C Neumann, Donna M.; Cammarata, Amy; Backes, Gregory; Palmer, Glen E.; Jursic, Branko S.; Bioorganic and Medicinal Chemistry; vol. 22; nb. 2; (2014); p. 813 - 826 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 - 20 °C Zhao, Xia; Zhang, Lipeng; Li, Tianjiao; Liu, Guiyan; Wang, Haomeng; Lu, Kui; Chemical Communications; vol. 50; nb.

86; (2014); p. 13121 - 13123 View in Reaxys 2.3. General procedure for the synthesis of Sulfonyl hydrazide General procedure: Sulfonyl hydrazides were prepared following the Scheme 1.Weighed amount of aromatic sulfonyl chloride was first dissolvedin tetrahydrofuran (5 mL) in a round bottom flask and cooled tobelow 5 C. Excess amount of Hydrazine hydrate (4:1) wasappended to the solution of aromatic sulfonyl chloride in the form of drops and maintained at temperature < 5 C during addition.This mixture was stirred for half an hour after the complete additionof hydrazine hydrate and was later transferred to a separatingfunnel to obtain two separate layers. The upper layer containingorganic solvent (tetrahydrofuran) and the product (sulfonyl hydrazide)was separated and stirred vigorously with cold distilledwater, which precipitated out fluffy white crystalline needles ofsulfonyl hydrazide (1-3) that were laterwashed with distilledwaterand dried at room temperature.

With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 5 °C Murtaza, Shahzad; Shamim, Saima; Kousar, Naghmana; Tahir, Muhammad Nawaz; Sirajuddin, Muhammad; Rana, Usman Ali; Journal of Molecular Structure; vol. 1107; (2016); p. 99 - 108 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 - 20 °C Yotphan, Sirilata; Sumunnee, Ladawan; Beukeaw, Danupat; Buathongjan, Chonchanok; Reutrakul, Vichai; Organic and Biomolecular Chemistry; vol. 14; nb. 2; (2015); p. 590 - 597

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

View in Reaxys Benzhydrazides (1a) and p-toluenesulfonylhydrazide (1e) have been synthesized by adding (10 mmol) of 50 percent hydrazine hydrate with benzoyl chloride (1 mmol) and p-toluenesulfonyl chloride (1 mmol) respectively under reflux for 0.5 h. The solid products were collected after cooling and dried.

With hydrazine hydrate, Time= 0.5h, Reflux Alsaeedi, Huda S.; Aljaber, Nabila A.; Ara, Ismet; Asian Journal of Chemistry; vol. 27; nb. 10; (2015); p. 3639 - 3646 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Liu, Congrong; Ding, Lianghui; Guo, Guang; Liu, Weiwei; European Journal of Organic Chemistry; vol. 2016; nb. 5; (2016); p. 910 - 912 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Liu, Congrong; Ding, Lianghui; Guo, Guang; Liu, Weiwei; Yang, Fu-Lai; Organic and Biomolecular Chemistry; vol. 14; nb.

10; (2016); p. 2824 - 2827 View in Reaxys With hydrazine hydrate in tetrahydrofuran, T= 0 °C Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Kalam Khan, Firoz A.; Sangshetti, Jaiprakash N.; Khedkar, Vijay M.; Shingate, Bapurao B.; New Journal of Chemistry; vol. 40; nb. 4; (2016); p. 3047 - 3058 View in Reaxys General method for the synthesis of compounds 4a-l General procedure: The sulfonylhydrazides 4a-l were prepared in excellentyields by adding the corresponding arylsulfonyl chloridesdissolved in THF to a slightly excess of hydrazine hydratesolution 80 percent, according to the procedure described in theliterature (Audrieth and Brhuchitsch 1956).

With hydrazine hydrate Nie, Yousong; Zhong, Min; Jiang, Zhiyuan; Sun, Jian; Gao, Yangguang; Ding, Fei; Li, Hang; Zhang, Yongmin; He, Xianran; Medicinal Chemistry Research; vol. 25; nb. 7; (2016); p. 1425 - 1432 View in Reaxys With hydrazine hydrate in benzene, T= 60 - 70 °C Leng, Yan-Li; Zhang, Jian-Hui; Li, Qiao; Zhang, You-Ming; Lin, Qi; Yao, Hong; Wei, Tai-Bao; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 191; nb. 10; (2016); p. 1318 - 1323 View in Reaxys Synthesis of 4-substituted phenylsulfonyl hydrazides General procedure: 0.01 mol 4-substituted phenylsulfonyl chloride was addedinto 0.04 mol hydrazine monohydrate in dichloromethanedropwise, stirred at room temperature and monitored byTLC after dichloromethane was distilled off and the crudeproduct was washed with water and hexane (Siemannet al., 2002; Kummerle et al., 2012).

With hydrazine hydrate in dichloromethane, T= 20 °C Karaman, Nurcan; Oruç-Emre, Emine Elçin; Sıcak, Yusuf; Çatıkkaş, Berna; Karaküçük-İyidoğan, Ayşegül; Öztürk, Mehmet; Medicinal Chemistry Research; vol. 25; nb. 8; (2016); p. 1590 - 1607 View in Reaxys With hydrazine hydrate in tetrahydrofuran, T= 20 °C Lu, Chuan-Jun; Chen, Hong; Chen, Dong-Kai; Wang, Hong; Yang, Zhen-Ping; Gao, Jianrong; Jin, Hongwei; Organic and Biomolecular Chemistry; vol. 14; nb. 46; (2016); p. 10833 - 10839 View in Reaxys With hydrazine hydrate in tetrahydrofuran, water, Time= 0.5h, T= 0 °C Jha, Abadh Kishor; Jain, Nidhi; Chemical Communications; vol. 52; nb. 9; (2016); p. 1831 - 1834

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Shinde, Popat S.; Patil, Nitin T.; European Journal of Organic Chemistry; vol. 2017; nb. 24; (2017); p. 3512 - 3515 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere, Schlenk technique Qian, Liang-Wei; Sun, Mengli; Dong, Jianyu; Xu, Qing; Zhou, Yongbo; Yin, Shuang-Feng; Journal of Organic Chemistry; vol. 82; nb. 13; (2017); p. 6764 - 6769 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Yang, Yu; Bao, Yajie; Guan, Qianqian; Sun, Qi; Zha, Zhenggen; Wang, Zhiyong; Green Chemistry; vol. 19; nb. 1; (2017); p. 112 - 116 View in Reaxys 158 mg

2.1 :take 1 mmol of 4-methylbenzenesulfonyl chloride (about 190 mg of), 1 mmol of hydrazine hydrate (about 50 l) reactor in pear-shaped flask, the reaction solvent is distilled water, stirred at room temperature, thin layer chromatography (TLC) tracking progress of the reaction, the reaction solution was poured into the reaction after a certain amount of cold water, the solid was filtered, washed, yielding intermediate (2-1) of approximately 158mg.

With hydrazine hydrate in water, T= 20 °C Patent; Sichuan People Hospital; Shi Jianyou; (21 pag.); CN106957242; (2017); (A) Chinese View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.416667h, T= 0 °C Li, Wei; Gao, Lingfeng; Zhuge, Wenyun; Sun, Xu; Zheng, Gengxiu; Organic and Biomolecular Chemistry; vol. 15; nb. 37; (2017); p. 7819 - 7823 View in Reaxys General procedures for the preparation of sulfonylhydrazides[19] General procedure: Hydrazine monohydrate (2.5 mmol) was added dropwise to a solution of an arylsulfonyl chloride (1.0 mmol) in THF (4 mL) under nitrogen at 0 °C. During the addition, the mixture became brown and a white precipitate of hydrazine hydrochloride was deposited. The mixture was stirred at 0 °C for 30 min, added ethyl acetate (120 mL), and washed with saturated brine (3 10 mL). The organic layer was dried over sodium sulfate, filtered, and added slowly to stirred hexane (25 mL) over 5 min. After being stirred for 10 min, the mixture was filtered, and the collected solid was dried in vacuum. The yields for the formation of sulfonylhydrazides range from 62 to 73percent.

With hydrazine hydrate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Tong, Chuo; Gan, Bing; Yan, Yiyan; Xie, Yuan-Yuan; Synthetic Communications; vol. 47; nb. 21; (2017); p. 1927 - 1933 View in Reaxys 3. General procedure for the synthesis of substituted sulfonyl hydrazides [30].

General procedure: Hydrazine hydrate (0.25 mol, 2.5 equiv) was added dropwise to a solution of p-toluene sulfonyl chloride or 2, 4, 6 trimethyl benzene sulfonyl chloride (0.1 mol, 1 equiv) in THF (100 mL) at 0 °C under an inert atmosphere. After stirring for 0 to 5 °C for 30 min, ice-cold ethyl acetate (200 mL) was added to the cooled reaction mixture and the mixture was washed repeatedly with ice cold 10percent aqueous sodium chloride (5 x 150 mL). The organic layer was dried over sodium sulfate at 0 °C, and was then added slowly to a stirring solution of hexane (1.2 L) during 5 min. Substituted benzene sulfonyl hydrazide precipitated as a white solid and was collected by vacuum filtration. The filter cake was washed with hexanes (2 x 50 mL) and then dried in vacuo yielding the title compound as a white solid (17.61 g, 81percent).

With hydrazine hydrate in tetrahydrofuran, T= 0 - 5 °C , Inert atmosphere Rajput, Jamatsing D.; Bagul, Suresh D.; Bendre, Ratnamala S.; Research on Chemical Intermediates; vol. 43; nb. 11; (2017); p. 6601 - 6616 View in Reaxys With hydrazine hydrate in tetrahydrofuran, water, Time= 0.5h, T= 0 °C

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Choudhuri, Khokan; Achar, Tapas Kumar; Mal, Prasenjit; Advanced Synthesis and Catalysis; vol. 359; nb. 20; (2017); p.

3566 - 3576 View in Reaxys With hydrazine hydrate in tetrahydrofuran, Time= 0.25h, T= 10 °C Sheykhan; Khani; Abbasnia; Shaabanzadeh; Joafshan; Green Chemistry; vol. 19; nb. 24; (2017); p. 5940 - 5948 View in Reaxys With hydrazine hydrate, T= 25 °C Queen, Aarfa; Khan, Parvez; Idrees, Danish; Azam, Amir; Hassan, Md. Imtaiyaz; International Journal of Biological Macromolecules; vol. 106; (2018); p. 840 - 850 View in Reaxys 35 : Example 35: Synthesis of p-toluenesulfonylhydrazide Hydrazine hydrate (7.87 g, 0.157 mol) was dissolved in 60 ml of water, cooled to 0° C., p-toluenesulfonyl chloride (3 g, 157 mmol) was dissolved in 10 ml of tetrahydrofuran, slowly added dropwise to the water, kept at 0° C. for one hour, and evaporated for most of the time. Tetrahydrofuran (non-heatable) precipitates a white powder that is a product, which can be filtered and dried With hydrazine hydrate in tetrahydrofuran, water, Time= 1h, T= 0 °C Patent; Soochow University (Suzhou); Li Huanqiu; Zhou Zehao; Huang Jun; Chen Xihua; (19 pag.); CN107759532; (2018); (A) Chinese View in Reaxys With hydrazine hydrate in tetrahydrofuran, water, Time= 0.5h, T= 0 °C Wu, Xiangmei; Wang, Yan; New Journal of Chemistry; vol. 42; nb. 13; (2018); p. 10953 - 10957 View in Reaxys

O O

H 2N

S

NH O

HO

S O

Rx-ID: 41155010 View in Reaxys 2/11 Yield 94 %

Conditions & References 17 :General procedure: 7.6 g (100.0 mmol) of solid hydrazine (H3N + NHCO2-) and adipic acid (7.3 g, 50.0 mmol) were mixed in a mortar without a solvent for 10 minutes and stirred at 100 ° C for 5 hours. To confirm the structure and composition of the product produced in this process and analyzed using 400 MHz NMR (nuclear magnetic resonance) and elemental analysis) .As a result of the analysis, the product was adipohydrazide (C6H14N4O2), the conversion rate was 96percent or more, and the yield was 95percent or more. Yield (8.27 g, 96percent or more); The product was obtained in the same manner as in Example 1 except that 17.21 g of 4-methylbenzenesulfonic acid was used instead of adipic acid. As a result of the analysis, the product was 4methylbenzenesulfono-hydrazide, the selectivity was 96percent or more, and the yield was 94percent. Yield: (17.48 g, 94percent); With carbazic acid in neat (no solvent), Time= 5h, T= 100 °C , Green chemistry Patent; Sogang University Academic Cooperation; Haw, Nam Hwe; Lee, Byung Noh; (24 pag.); KR2015/88523; (2015); (A) Korean View in Reaxys Reaction Steps: 2 1: triethylamine / acetonitrile / 0.01 h / 20 °C / Sonication 2: hydrazine hydrate / 0.02 h / Sonication With hydrazine hydrate, triethylamine in acetonitrile Khan, Khalid Mohammed; Salar, Uzma; Fakhri, Muhammad Imran; Taha, Muhammad; Hameed, Abdul; Perveen, Shahnaz; Voelter, Wolfgang; Letters in Organic Chemistry; vol. 12; nb. 9; (2015); p. 637 - 644 View in Reaxys

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

H 2N

O

NH

S O

O N

S O

N

Rx-ID: 41155036 View in Reaxys 3/11 Yield

Conditions & References 4.2. general procedure for the syntheses of acyl/sulfonly hydrazines General procedure: In a 100 mL round-bottom flask, benzoic acid 1 (0.122 g= 1 mmol) / benzene sulfonic acid 18 (0.152 g = 1 mmol),and triethylamine (0.1 ml = 1.2 mmol) in acetonitrile (10mL) were taken. 1,1-carbonyldiimidazole (0.162 g = 1mmol) was added to the above-mentioned mixture and reflux for 15 to 30 min. Acyl imidazole formation was confirmedby TLC monitoring. Then, hydrazine hydrate 55percent (SigmaAldrich) (1 mL) was added into the reaction mixture andfurther reflux for 2-4 h. After completion (TLC monitoring), the reaction mixture was poured onto crushed ice, formed precipitates were filtered and washed with plenty of distilled water and then with hexane. The crude products were recrystallized from ethyl acetate and hexane.

With hydrazine hydrate, Time= 0.0166667h, Sonication Khan, Khalid Mohammed; Salar, Uzma; Fakhri, Muhammad Imran; Taha, Muhammad; Hameed, Abdul; Perveen, Shahnaz; Voelter, Wolfgang; Letters in Organic Chemistry; vol. 12; nb. 9; (2015); p. 637 - 644 View in Reaxys O

O

H 2N

S N

NH

NH

S

O

O

Rx-ID: 11270924 View in Reaxys 4/11 Yield

Conditions & References With water in phosphate buffer, ethanol, T= 25 °C , pH= 2.47, Kinetics, Further Variations: pH-values Levrand, Barbara; Fieber, Wolfgang; Lehn, Jean-Marie; Herrmann, Andreas; Helvetica Chimica Acta; vol. 90; nb. 12; (2007); p. 2281 - 2314 View in Reaxys O

O S HN

H 2N

NH

NH

O

O

S O

O

Rx-ID: 25923970 View in Reaxys 5/11 Yield 78 %

Conditions & References With trifluoroacetic acid, Time= 0.5h Safaei-Ghomi, Javad; Journal of the Chinese Chemical Society; vol. 54; nb. 6; (2007); p. 1561 - 1563 View in Reaxys O

O S N

H 2N

H

NH

NH

O O

S O

Rx-ID: 25678288 View in Reaxys 6/11

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Yield

Conditions & References 2.c; 2.e :All reactions were carried out in quartz cuvettes (1 cm) by adding either 0.2 ml of hydrazine derivative and 0.2 ml of cinnamic aldehyde (CA) or benzaldehyde (BA) (all at 2.0 x 10"4 M in ethanol) to 2 ml of the buffer stock solution prepared above or, alternatively, by adding 0.4 ml of the corresponding hydrazone (at 1.0 X 10"4 M in ethanol) to 2 ml of the buffer stock solution. UV/Vis spectra were recorded at constant time intervals between 240 and 450 nm. The first spectrum was recorded 2-3 min after addition of the compounds to the buffer solution, the following spectra were taken at intervals of 5 or 10 min (pH 2.47) or 30 or 60 min (pH 4.48), respectively. If complete hydrolysis of the hydrazone takes place, the UV absorption at a given wavelength should change from that of the pure hydrazone (Ah) to reach the one corresponding to the mixture of the hydrazine derivative and the aldehyde/ketone (Aa+ti)- The inverse is expected for the formation of the hydrazone from the corresponding aldehyde/ketone and a hydrazine derivative. If in the course of the reaction the absorption approaches a constant value lying between these two extrema,an equilibrium state is reached and an "equihbrium value" xeq can be defined, which indicates to which point the reaction proceeds in either direction at a given wavelengthV-Aa+h Ah-VFor a given dynamic mixture xeq^ is the equilibrium value for the formation of the dynamic mixture by contacting a hydrazine derivative with the aldehyde or ketone in water, xeq /. the equilibrium value for the dynamic mixture by contacting the hydrazone derivative with water, and Aeq is the absorption reached at the equilibrium. Under the conditions described above, the formation of a dynamic mixture either by hydrolysis of the hydrazone (lc, 2c, 2b or 14b) or by reaction between the hydrazine derivative (la, 2a or 14a) and benzaldehyde or cinnamic aldehyde, respectively, gave the following equilibrium values xeq at 1=290 nm (BA) or 1-320 nm (CA):Equilibriui between t and the alen formation via reaction le hydrazine derivative ehydeEquilibrium formation via hydrolysis of the hydrazonehydrazine +aldehydex f AeqpH = 2.47x f AeqpH = 4.48hydrazonex kAeqpH = 2.47x h pH = 4.48la + BA0.09lb0.13la + CA0.280.50lc0.330.522a + BA0.192b0.212a + CA0.42 .0.642c0.440.6314a+ BA0.1814b0.20If the values for Xeq are both either 1 or 0, the hydrazone formation or the hydrazone hydrolysis go to completion, respectively. As can be noticed, the mixtures are the result of reversible reactions between various starting components, as the measured "equilibrium values" xeq are larger than 0 and smaller than 1.Within the experimental error of the measurements, of approximately +/- 0.1, the same equilibrium state is reached independently of the stating point (i.e. hydrazine derivative, aldehyde and water or hydrazone and water).It may happen, for other active aldehydes/ketones or hydrazine derivatives, that the equilibration is relatively slow, and that within the timeframe of the experiment such equilibrium is not fully reached, but this does not imply that the dynamic mixtures obtained by either contacting the hydrazine derivative and the active compound in water or by contacting the hydrazone derivative and water are not the same.The UV/Vis spectra recorded for the formation and hydrolysis of hydrazone derivative lc are shown in Figure (I).; e) Determination of the rate constants for the formation of dynamic mixtures by contacting hydrazone derivatives and waterThe UV/Vis spectra were recorded and the rate constants determined as described above to give the following values for the hydrolysis of hydrazones:HydrazoneActive aldehyde or ketoneRate constant inphosphoric acidbuffer at pH = 2.47h Ts"1.Rate constant incitric acid buffer atpH = 4.48h rs4] lbbenzaldehyde1.1 xlO"33.0 x 10"5lccinnamic aldehyde3.3 XlO"4 .1.5 x 10"52bbenzaldehyde6.4 xlO"41.8 XlO"52ccinnamic aldehyde2.1 x 10"48.5 X 10"62dvanillin6.6 x 10"43ccinnamic aldehyde2.3 x 10"46.9 XlO"64bbenzaldehyde5.0 XlO"49.0 XlO"64ccinnamic aldehyde6.3 x 10"65bbenzaldehyde2.2 xlO"45ccinnamic aldehyde5.7 x 10"66bbenzaldehyde7.5 X10"56ccinnamic aldehyde1.7xl0"5a)8bbenzaldehyde3.6 x 10"5 b)8dacetophenone1.5 XlO"40)1.0 xlO"50)14bbenzaldehyde1.1 X 10"34.3 x 10"514dvanillin9.8 X 10"415bbenzaldehyde6.4 XlO"418ccinnamic aldehyde1.8 XlO"5 a) r2 ca. 0.97, At = 5 h; b) r2 > 0.98, At = 3.8 h, detection at 270 nm; c) detection at 270 nm.

With water in ethanol, Time= 3.8h, pH= 2.47, Phosphoric acid buffer, Rate constant Patent; FIRMENICH SA; UNIVERSITE LOUIS PASTEUR; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; WO2006/16248; (2006); (A1) English View in Reaxys

H 2N

NH

O

O

S

N N H

O

S O

O

Rx-ID: 25685126 View in Reaxys 7/11 Yield

Conditions & References 2.c; 2.e :All reactions were carried out in quartz cuvettes (1 cm) by adding either 0.2 ml of hydrazine derivative and 0.2 ml of cinnamic aldehyde (CA) or benzaldehyde (BA) (all at 2.0 x 10"4 M in ethanol) to 2 ml of the buffer stock solution prepared above or, alternatively, by adding 0.4 ml of the corresponding hydrazone (at 1.0 X 10"4 M in ethanol) to 2 ml of the buffer stock solution. UV/Vis spectra were recorded at constant time intervals between 240 and 450 nm. The first spectrum was recorded 2-3 min after addition of the compounds to the buffer solution, the following spectra were taken at intervals of 5 or 10 min (pH 2.47)

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

or 30 or 60 min (pH 4.48), respectively. If complete hydrolysis of the hydrazone takes place, the UV absorption at a given wavelength should change from that of the pure hydrazone (Ah) to reach the one corresponding to the mixture of the hydrazine derivative and the aldehyde/ketone (Aa+ti)- The inverse is expected for the formation of the hydrazone from the corresponding aldehyde/ketone and a hydrazine derivative. If in the course of the reaction the absorption approaches a constant value lying between these two extrema,an equilibrium state is reached and an "equihbrium value" xeq can be defined, which indicates to which point the reaction proceeds in either direction at a given wavelengthV-Aa+h Ah-VFor a given dynamic mixture xeq^ is the equilibrium value for the formation of the dynamic mixture by contacting a hydrazine derivative with the aldehyde or ketone in water, xeq /. the equilibrium value for the dynamic mixture by contacting the hydrazone derivative with water, and Aeq is the absorption reached at the equilibrium. Under the conditions described above, the formation of a dynamic mixture either by hydrolysis of the hydrazone (lc, 2c, 2b or 14b) or by reaction between the hydrazine derivative (la, 2a or 14a) and benzaldehyde or cinnamic aldehyde, respectively, gave the following equilibrium values xeq at 1=290 nm (BA) or 1-320 nm (CA):Equilibriui between t and the alen formation via reaction le hydrazine derivative ehydeEquilibrium formation via hydrolysis of the hydrazonehydrazine +aldehydex f AeqpH = 2.47x f AeqpH = 4.48hydrazonex kAeqpH = 2.47x h pH = 4.48la + BA0.09lb0.13la + CA0.280.50lc0.330.522a + BA0.192b0.212a + CA0.42 .0.642c0.440.6314a+ BA0.1814b0.20If the values for Xeq are both either 1 or 0, the hydrazone formation or the hydrazone hydrolysis go to completion, respectively. As can be noticed, the mixtures are the result of reversible reactions between various starting components, as the measured "equilibrium values" xeq are larger than 0 and smaller than 1.Within the experimental error of the measurements, of approximately +/- 0.1, the same equilibrium state is reached independently of the stating point (i.e. hydrazine derivative, aldehyde and water or hydrazone and water).It may happen, for other active aldehydes/ketones or hydrazine derivatives, that the equilibration is relatively slow, and that within the timeframe of the experiment such equilibrium is not fully reached, but this does not imply that the dynamic mixtures obtained by either contacting the hydrazine derivative and the active compound in water or by contacting the hydrazone derivative and water are not the same.The UV/Vis spectra recorded for the formation and hydrolysis of hydrazone derivative lc are shown in Figure (I).; e) Determination of the rate constants for the formation of dynamic mixtures by contacting hydrazone derivatives and waterThe UV/Vis spectra were recorded and the rate constants determined as described above to give the following values for the hydrolysis of hydrazones:HydrazoneActive aldehyde or ketoneRate constant inphosphoric acidbuffer at pH = 2.47h Ts"1.Rate constant incitric acid buffer atpH = 4.48h rs4] lbbenzaldehyde1.1 xlO"33.0 x 10"5lccinnamic aldehyde3.3 XlO"4 .1.5 x 10"52bbenzaldehyde6.4 xlO"41.8 XlO"52ccinnamic aldehyde2.1 x 10"48.5 X 10"62dvanillin6.6 x 10"43ccinnamic aldehyde2.3 x 10"46.9 XlO"64bbenzaldehyde5.0 XlO"49.0 XlO"64ccinnamic aldehyde6.3 x 10"65bbenzaldehyde2.2 xlO"45ccinnamic aldehyde5.7 x 10"66bbenzaldehyde7.5 X10"56ccinnamic aldehyde1.7xl0"5a)8bbenzaldehyde3.6 x 10"5 b)8dacetophenone1.5 XlO"40)1.0 xlO"50)14bbenzaldehyde1.1 X 10"34.3 x 10"514dvanillin9.8 X 10"415bbenzaldehyde6.4 XlO"418ccinnamic aldehyde1.8 XlO"5 a) r2 ca. 0.97, At = 5 h; b) r2 > 0.98, At = 3.8 h, detection at 270 nm; c) detection at 270 nm.

With water in ethanol, pH= 2.47, Phosphoric acid buffer, Rate constant Patent; FIRMENICH SA; UNIVERSITE LOUIS PASTEUR; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; WO2006/16248; (2006); (A1) English View in Reaxys 2.c; 2.e :All reactions were carried out in quartz cuvettes (1 cm) by adding either 0.2 ml of hydrazine derivative and 0.2 ml of cinnamic aldehyde (CA) or benzaldehyde (BA) (all at 2.0 x 10"4 M in ethanol) to 2 ml of the buffer stock solution prepared above or, alternatively, by adding 0.4 ml of the corresponding hydrazone (at 1.0 X 10"4 M in ethanol) to 2 ml of the buffer stock solution. UV/Vis spectra were recorded at constant time intervals between 240 and 450 nm. The first spectrum was recorded 2-3 min after addition of the compounds to the buffer solution, the following spectra were taken at intervals of 5 or 10 min (pH 2.47) or 30 or 60 min (pH 4.48), respectively. If complete hydrolysis of the hydrazone takes place, the UV absorption at a given wavelength should change from that of the pure hydrazone (Ah) to reach the one corresponding to the mixture of the hydrazine derivative and the aldehyde/ketone (Aa+ti)- The inverse is expected for the formation of the hydrazone from the corresponding aldehyde/ketone and a hydrazine derivative. If in the course of the reaction the absorption approaches a constant value lying between these two extrema,an equilibrium state is reached and an "equihbrium value" xeq can be defined, which indicates to which point the reaction proceeds in either direction at a given wavelengthV-Aa+h Ah-VFor a given dynamic mixture xeq^ is the equilibrium value for the formation of the dynamic mixture by contacting a hydrazine derivative with the aldehyde or ketone in water, xeq /. the equilibrium value for the dynamic mixture by contacting the hydrazone derivative with water, and Aeq is the absorption reached at the equilibrium. Under the conditions described above, the formation of a dynamic mixture either by hydrolysis of the hydrazone (lc, 2c, 2b or 14b) or by reaction between the hydrazine derivative (la, 2a or 14a) and benzaldehyde or cinnamic aldehyde, respectively, gave the following equilibrium values xeq at 1=290 nm (BA) or 1-320 nm (CA):Equilibriui between t and the alen formation via reaction le hydrazine derivative ehydeEquilibrium formation via hydrolysis of the hydrazonehydrazine +aldehydex f AeqpH = 2.47x f AeqpH = 4.48hydrazonex kAeqpH = 2.47x h pH = 4.48la + BA0.09lb0.13la + CA0.280.50lc0.330.522a + BA0.192b0.212a + CA0.42 .0.642c0.440.6314a+ BA0.1814b0.20If the values for Xeq are both either 1 or 0, the hydrazone formation or the hydrazone hydrolysis go to completion, respectively. As can be noticed, the mixtures are the result of reversible reactions between various starting components, as the measured "equilibrium values" xeq are larger than 0 and smaller than

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

1.Within the experimental error of the measurements, of approximately +/- 0.1, the same equilibrium state is reached independently of the stating point (i.e. hydrazine derivative, aldehyde and water or hydrazone and water).It may happen, for other active aldehydes/ketones or hydrazine derivatives, that the equilibration is relatively slow, and that within the timeframe of the experiment such equilibrium is not fully reached, but this does not imply that the dynamic mixtures obtained by either contacting the hydrazine derivative and the active compound in water or by contacting the hydrazone derivative and water are not the same.The UV/Vis spectra recorded for the formation and hydrolysis of hydrazone derivative lc are shown in Figure (I).; e) Determination of the rate constants for the formation of dynamic mixtures by contacting hydrazone derivatives and waterThe UV/Vis spectra were recorded and the rate constants determined as described above to give the following values for the hydrolysis of hydrazones:HydrazoneActive aldehyde or ketoneRate constant inphosphoric acidbuffer at pH = 2.47h Ts"1.Rate constant incitric acid buffer atpH = 4.48h rs4] lbbenzaldehyde1.1 xlO"33.0 x 10"5lccinnamic aldehyde3.3 XlO"4 .1.5 x 10"52bbenzaldehyde6.4 xlO"41.8 XlO"52ccinnamic aldehyde2.1 x 10"48.5 X 10"62dvanillin6.6 x 10"43ccinnamic aldehyde2.3 x 10"46.9 XlO"64bbenzaldehyde5.0 XlO"49.0 XlO"64ccinnamic aldehyde6.3 x 10"65bbenzaldehyde2.2 xlO"45ccinnamic aldehyde5.7 x 10"66bbenzaldehyde7.5 X10"56ccinnamic aldehyde1.7xl0"5a)8bbenzaldehyde3.6 x 10"5 b)8dacetophenone1.5 XlO"40)1.0 xlO"50)14bbenzaldehyde1.1 X 10"34.3 x 10"514dvanillin9.8 X 10"415bbenzaldehyde6.4 XlO"418ccinnamic aldehyde1.8 XlO"5 a) r2 ca. 0.97, At = 5 h; b) r2 > 0.98, At = 3.8 h, detection at 270 nm; c) detection at 270 nm.

With water in ethanol, pH= 4.48, Citric acid buffer, Rate constant Patent; FIRMENICH SA; UNIVERSITE LOUIS PASTEUR; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; WO2006/16248; (2006); (A1) English View in Reaxys H 2N

NH O

S O

Rx-ID: 5934917 View in Reaxys 8/11 Yield

Conditions & References Freeman,P.K.; Johnson,R.C.; Journal of Organic Chemistry; vol. 34; (1969); p. 1751 - 1759 View in Reaxys Baldwin,J.E.; Krauss,H.C.; Journal of Organic Chemistry; vol. 35; nb. 7; (1970); p. 2426 View in Reaxys Joshi et al.; Journal of Heterocyclic Chemistry; vol. 16; (1979); p. 1141,1142, 1145 View in Reaxys Patent; Hoffmann-LaRoche; DE1132142; (1959); GB867985; ; nb. 25722; (1961) View in Reaxys De Puy et al.; Journal of the American Chemical Society; vol. 82; (1960); p. 631 View in Reaxys Jacobson; Chemica Scripta; vol. 2; (1972); p. 127,129 View in Reaxys Munshi et al.; Indian Journal of Chemistry; vol. 1; (1963); p. 311,312 View in Reaxys Dshidshelawa et al.; J. Gen. Chem. USSR (Engl. Transl.); vol. 35; (1965); p. 831,834 View in Reaxys Litwinenko et al.; J. Gen. Chem. USSR (Engl. Transl.); vol. 34; (1964); p. 3730,3780 View in Reaxys Patent; U.S.Rubber Co.; NL6515582; (1964); ; vol. 65; nb. 18534a; (1966) View in Reaxys Kascheres; van Fossen Bravo; Organic Mass Spectrometry; vol. 14; (1979); p. 293,294 View in Reaxys As specific examples of hydrazine sulfonate compounds, ... bis(p-toluenesulfonyl)hydrazine, bis(trifluoromethanesulfonyl)hydrazine, bis(nonafluoro-n-butanesulfonyl)hydrazine, bis(n-propanesulfonyl)hydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, trifluoromethanesulfonylhydrazine, nonafluoro-n-butanesulfonylhydrazine, n-propanesulfonylhydrazine, and

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

Patent; Nagai, Tomoki; Shimokawa, Tsutomu; US2003/194634; (2003); (A1) English View in Reaxys As specific examples of hydrazine sulfonate compounds, ... bis(p-toluenesulfonyl)hydrazine, bis(trifluoromethanesulfonyl)hydrazine, bis(pentafluoroethanesulfonyl)hydrazine, bis(n-propanesulfonyl)hydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, trifluoromethanesulfonylhydrazine, pentafluoroethanesulfonylhydrazine, n-propanesulfonylhydrazine, and Patent; Nagai, Tomoki; Numata, Jun; Kusumoto, Shirou; Kobayashi, Eiichi; US2002/172885; (2002); (A1) English View in Reaxys 2 : EXAMPLE 2 EXAMPLE 2 In 2 l of methanol was dissolved 1 mole (165 g) of chloral hydrate.

To the resulting solution under stirring was added 1 mole (186 g) of p-toluenesulfohydrazide in the form of powder at room temperature over around 2 minutes followed by further stirring at room temperature for one hour to subject the chloral hydrate and the p-toluenesulfohydrazide to reaction.

Patent; UBE Industries, Ltd.; US4594424; (1986); (A) English View in Reaxys 5 : EXAMPLE 5 EXAMPLE 5 In 2 l of methanol was dissolved 1 mole (165 g) of chloral hydrate.

To the resulting solution with stirring was added 1 mole (186 g) of p-toluenesulfohydrazide in the form of powder at room temperature over around 2 minutes, and the mixture was further stirred at room temperature for 1 hour to subject the chloral hydrate and the p-toluenesulfohydrazide to reaction.

Patent; UBE Industries, Ltd.; US4594424; (1986); (A) English View in Reaxys 6 : EXAMPLE 6 EXAMPLE 6 In 2 l of methanol was dissolved 1 mole (146 g) of chloral.

To the stirred resulting solution was added 1 mole (186 g) of p-toluenesulfohydrazide in the form of powder at room temperature over around 5 minutes followed by further stirring at room temperature for 1 hour to subject the chloral and the p-toluenesulfohydrazide to reaction.

Patent; UBE Industries, Ltd.; US4594424; (1986); (A) English View in Reaxys O

O O

O N

S

H 2N

NH 2

NH HN

N

O N O

O

N

S HN N

O

NH

O O

NH 2

Rx-ID: 3469819 View in Reaxys 9/11 Yield 76 %

Conditions & References With hydrazine hydrate in ethanol, 1.) reflux, 2 h, 2.) from 150 deg C to 200 deg C, 20 min.

Tominaga, Yoshinori; Luo, Jiann-Kuan; Castle, Lyle W.; Castle, Raymond N.; Journal of Heterocyclic Chemistry; vol. 30; nb. 1; (1993); p. 267 - 273 View in Reaxys

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4-Methylbenzenesulfonhydrazide (TsNHNH2) [C7H10N2O2S]

H 2N

O

OH

O

S

NH O

Cl

S O

Rx-ID: 3428057 View in Reaxys 10/11 Yield

Conditions & References With hydrazine, T= 21 °C , Rate constant Oae, Shigeru; Kadoma, Yoshihito; Canadian Journal of Chemistry; vol. 64; (1986); p. 1184 - 1188 View in Reaxys

O

N O

O

NH

O

H 2N

NH

O O

S

O

O

S O

Rx-ID: 25059803 View in Reaxys 11/11 Yield

Conditions & References 170 : 2S,3R-3-Acetoxy-6-(2-acetoxyethylidene)-2-methyl-2-(4,8-dimethyl-5-p-toluenesulfonylhydrazono-7-nonenyl)-oxepane EXAMPLE 170 2S,3R-3-Acetoxy-6-(2-acetoxyethylidene)-2-methyl-2-(4,8-dimethyl-5-p-toluenesulfonylhydrazono-7-nonenyl)-oxepane Following the procedure of Example 124 but substituting an equivalent amount of p-toluenesulfonylhydrazide for p-bromobenzenesulfonylhydrazide, 2S,3R-3-acetoxy-6-(2-acetoxyethylidene)-2-methyl-2-(4,8-dimethyl-5-p-toluenesulfonylhydrazono-7nonenyl)-oxepane is obtained.

Patent; Ortho Pharmaceutical Corporation; US4408060; (1983); (A) English View in Reaxys

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