foxy2
(Distinctive Doe)
12-03-01 03:30
No 243547
      Hydrazine Info Ect.
(Rated as: excellent)
 Bookmark   

Here are some other Hydrazine threads
Post 55738 (halfapint: "Re: Hydrazine, and substitutable amines.", Tryptamine Chemistry) Post 106321 (Osmium: "Re: Hydrazine from hydrazine sulfate", Chemistry Discourse) Post 225854 (Rhodium: "Hydrazine Sulfate", Tryptamine Chemistry)

Ok a new synthesis, this first reference looks like one you MUST have if you want to work with this reagent.

Safe handling and purification of aqueous hydrazine.
Mitchell, J. W.; Harris, T. D.; Blitzer, L. D.
Anal. Chem.  (1980),  52(4),  774-6.
Abstract
Procedures are described for the safe handling and purifn. of aq. N2H4 solns.  The purity of this reagent, prepd. by low temp. sublimation, was compared to other available reducing agents with the essential chem. and phys. properties for general use in anal. redns.  Analyses by flameless at. absorption spectroscopy indicate that the prepd. N2H4 reagent is the purest, aq. phase, general purpose, anal. reducing agent currently known.


Hydrazine from urea.    
West, Joseph Sidney.   
Brit.  (1969), GB 1153483  19690529 
 Abstract
N2H4 is made by the reaction of (NH2)2CO, NaOCl, and NaOH in 2 stages by using only a slight excess of NaOH.  In the 1st stage concd. solns. of (NH2)2CO 1.0-1.1, NaOCl 1.0, and NaOH 0.1-0.3 moles are reacted at -10 to 10 to give NH2CONHCl.  In the 2nd stage this is reacted with more NaOH (total 1.9-2.1 moles) at 90-110 in the presence of 0.2-1.0% of gelatin or glue. The 2nd stage is carried out with a small residence time, e.g. 30-60 sec. at 100.  Thus, 126 g. (2.1 moles) (NH2)2CO was dissolved in 189 g. water and 8 g. 50% NaOH soln. were added; then 1244 g. (2.0 moles) of a 12% soln. of NaOCl were added to this over 1-2 hrs. at -5; after this 152 g. (3.8 moles) of NaOH as a 50% soln. and 1 g. of gelatin in 20 g. water were added and the mixt. was heated rapidly to 65-75.  The temp. then rose rapidly to 95-100 to give a 3.3% soln. of N2H4 in 75% yield.                   http://l2.espacenet.com/dips/viewer?PN=GB1153483&CY=ep&LG=en&DB=EPD

Continuous manufacture of hydrazine and of its salts. 
Popa, Oliviu; Popa, Elena C.
Rom.  (1973), RO  52528  19730330  Patent  written in Romanian.
Abstract
A continuous, time saving process, with higher yields is described in which cooling to 0 is unnecessary, 40% NaOH soln. is not used, and corrosion is reduced.  Aq. 18% NaOH 1900, Cl gas 100, and aq. 25% urea 105 kg/hr are mixed at 20.  The urea soln. contained the catalysts 0.04 kg gelatin with either 2 kg MgSO4 or 0.4 kg MnSO4.  Leaving the reactor at 95-100, the soln. contained 2.3-2.7% hydrazine hydrate, representing a 90% yield based on Cl, and was neutralized with 98% H2SO4 to ppt. hydrazine sulfate.


ALKALI CYCLING PROCESS FOR THE PRODUCTION OF HYDRATED HYDRAZINE
FROM UREA 
Patent Number: CN1046328  (Written in Chinese)
Abstract
This invention relates to an alkali circulating process used in the preparation of hydrated hydrazine with sodium hypochlorite under alkaline condition by using urea as raw material. The reaction liquid resulted in the preparation of hydrated hydrazine is causticized with calcium hydroxide, and sodium carbonate is converted into sodium hydroxide and calcium carbonate. After calcium carbonate is separated out, hydrated hydrazine, caustic soda and sodium chloride, being in gaseous, liquid and solid phase separately, are separated during distillation and separation of hydrated hydrazine. Sodium chloride is recovered, caustic soda solution is reused.


Modification of the urea process for production of hydrazine.    
Schoenbeck, Rupert; Kloimstein, Engelbert.
Chem.-Ing.-Tech.  (1974),  46(9),  391. Journal  written in German.
Abstract
The process involves prepn. of NaOCl by reaction of dil. NaOH soln. with Cl2 followed by treating the mixt. with a 40% urea soln.  After heating to .apprx.100 the hydrazine formed is extd. into Me isobutyl ketone and then into HCl.  The hydrazine hydrochloride soln. thus formed is  concd. by evapn.  The max. yield is 80%.


Isolation of hydrazine hydrate.    
Mundil, Rudolf.
Ger.  (1966), DE  1222900  19660818  Patent  written in German.
Abstract
Hydrazine hydrate (I) reaction soln., prepd. from NH3 and NaOCl, was passed into a rotary evaporator fitted with 2 bubble cap plates.  When the plates were charged with water, aq. I contg.  0.1-0.2 ppm. of chloride, and when charged with 5% NaOH, aq. I contg. 0.01% CO2, was obtained.


Separation of hydrazine from aqueous solutions.   
DE  2056357  19720518  Patent  written in German.
Abstract
N2H4, prepd. by reaction of Cl with NH3 via the chloramine in dil. aq.  solns., was isolated from these solns. by treatment with MeCOEt, EtCHO, or Me2CO in the presence of hydrophilic substances, e.g. NaCl or CaCl2, making the reaction products H2O-insol. and forming 2 phases, sepg. the reaction product phase, and reconverting the reaction products into N2H4 and carbonyl compns.  Thus, 200 ml NaCl-satd. soln. contg. 5.0 g N2H4.H2O was mixed with 50.8 g Me2CO at 50 to give a H2O-poor phase contg. 93.5% N2H4H2O.


Hydrazine and hydrazine hydrate.    
Schwarcz, Morton.    
US Patent 2537791  19510109
Abstract
N2H4 (I) or N2H4.H2O (II) are produced by a 1-step distn. in a reducing atm. of a mixt. of a hydrazine salt and an amine, especially the alkylene polyamines, which boil higher than I or II, whichever the case may be; H2O is added to the mixt. to yield any desired concn. of II.  Glycols, etc., may be added to reduce the viscosity of the distn. mixts.  Thus, N2H4.H2SO4 260, (CH2NHCH2CH2NH2)2 240, and H2O 20 g., stirred 1 hr. at 60 and distd., give 75.5 g. of approx. 100% II, b70 59-67. 

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    foxy2
(Distinctive Doe)
12-03-01 03:35
No 243550
      What to do with Hydrazine
(Rated as: excellent)
 Bookmark   

Hmmm, I would bet that Ushibara Nickel would substitute for Raney nickel in many of these reductions. smile
Enjoy
Foxy

Reduction of nitriles with hydrazine hydrate in the presence of Raney nickel.
Terent'ev, A. P.; Preobrazhenskaya, M. N.; Ge, Ban-Lun.
Khim. Nauka i Prom.  (1959),  4  281-2. 
Abstract
3-Indoleacetonitrile (I), 5-methoxy-2-methyl-1-benzyl-3-indoleacetonitrile (II), and phenylacetonitrile (III) reduced with N2H4.H2O (IV) in the presence of Raney Ni gave only the corresponding primary amines; secondary amines and derivs. of tetrazine or triazole did not form to any appreciable degree.  Adding 48 ml. IV in small portions to 2.56 g. hot (H2O bath) I in 50 ml. EtOH and 0.5 g. Raney Ni, heating till no more NH3 formed (1 hr.), filtering, and distg. H2O and EtOH in vacuo yielded 95% tryptamine, m. 113-14 (EtOH).  Similar treatment of II, with the addn. of C6H6 and 10% HCl after solvent distn., yielded 90% 5-methyl-1-benzyl-2-methyltryptamine-H Cl, m. 225-7.  III in BuOH gave 59% phenethylamine, b12 78-80.


Central stimulants-chemistry and structure activity relations of aralkyl hydrazines.    
Biel, John H.; Drukker, Alexander E.; Mitchell, Thomas F.;
J. Am. Chem. Soc.  (1959),  81  2805-13. 
Abstract
The replacement of an amino or alkylamino group by a hydrazine or alkyl hydrazine moiety in a variety of aralkylamines has yielded a group of potent central stimulants which produce their effect by a dual mechanism: (1) direct stimulation of the central nervous system (analeptic action), and (2) powerful inhibition of the enzyme monoamine oxidase which is responsible for the metabolic destruction of endogenous central excitatory hormones.  Structure-activity relations are established and discussed.  N-Aminoamphetamine displayed 40 times the monoamine oxidase inhibitory potency of iproniazid (Marsilid).  The synthesis of the aralkyl hydrazines was accomplished by the reductive hydrazinolysis of phenylalkanones or reaction of hydrazine with a phenylalkyl halide.  It is demonstrated that the Raney Ni cleavage of substituted hydrazines constitutes a convenient means of obtaining pure primary and secondary amines.


Reduction of oximes by hydrazine-Raney Ni.    
Lloyd, Douglas; McDougall, Ronald H.; Wasson, F. I.
J. Chem. Soc.  (1965),   (Jan.),  822-3. 
Abstract
The appropriate oxime (0.02 mole) and 6 cc. 64% N2H4.H2O in 50 cc. EtOH treated with Raney Ni W-4 sludge in portions to maintain a steady reaction, refluxed about 4 hrs., filtered, and treated with gaseous HCl gave the amine-HCl salt, or the reaction mixt. dild. with H2O gave the free (H2O-insol.) amine.  Mesityl oxide oxime (11.81 g.), 30 cc. 64% N2H4, and 100 cc. EtOH yielded 3,5,5-trimethylpyrazoline (I), b45 80-4.  By the general procedure were reduced the oximes of the following compds. (% corresponding amine given): Me2CO, 36; EtCOMe, 76; AcPr, 42; AcC9H19 9; cyclopentanone, 27; cyclohexanone, 65; cycloheptanone, 29; menthone, 90; carvomenthone, 36; dihydrocarvone, 8; fenchone, 6; camphor, 0; BzPh, 45; BzEt, 24; BzCH2Ph, 74; fluorenone, 94; 3-hydroxy-1,2-benzofluorenone, 97; (AcCH2)2, 31; C6H13CHO, 0; BzH, 0.  Isophorone and carvone gave similarly I.  AcC(:NOH)Me and [MeC(:NOH)]2CH2 gave Ni complexes.


Primary amines.    
Ottiger, Pius.  (Sandoz-Wander, Inc., USA).    U.S.  (1976)
US Patent 3959379
Abstract
HO(CH2)4CH:NOH (I) was reduced by H2NNH2 over Raney Ni to HO(CH2)5NH2; I was prepd. by acid cleavage of dihydropyran to HO(CH2)4CHO, which then reacted with H2NOH. 


A facile reduction of azides to amines using hydrazine.
Malik, A. A.; Preston, S. B.; Archibald, T. G.; Cohen, M. P.; Baum, K.   
Synthesis  (1989),   (6),  450-1.
Abstract
Alkyl and aryl azides were reduced to the amines in high yields by reaction with N2H4 in refluxing MeOH in the presence of Pd.


Catalytic reduction of aromatic nitro compounds with hydrazine hydrate in the presence of iron(III) oxide hydroxide.    
Miyata, Toshiyuki; Ishino, Yoshio; Hirashima, Tsuneaki.
Synthesis  (1978),   (11),  834-5.
Abstract
Arenamines, e.g., 4-RC6H4NH2 ( R = Me, H, MeO, NHz) 6-methoxy-o-phenylenediamine, 4-chloro-m-phenylenediamine, and 1-naphthylamine were prepd. in 65-92.5% yield by the title redn. in the presence of b-FeO(OH) or b-Fe2O3.H2O.  In the redn. of 4-O2NC6H4Me, 4-MeC6H4NOH was identified as an intermediate.


Nickel boride/hydrazine hydrate reduction of aromatic and aliphatic nitro compounds.  Synthesis of 4-(benzyloxy)indole and a-alkyltryptamines.    
Lloyd, David H.; Nichols, David E.       
J. Org. Chem.  (1986),  51(22),  4294-5.
Abstract
Nickel boride and hydrazine hydrate are convenient reagents for the redn. of arom. and aliph. nitro compds. to the corresponding amines.  The reductive cyclization of 2-(benzyloxy)-6-nitro-2'-piperidinostyrene to 4-(benzyloxy)indole and the redn. of several indole nitroalkanes to the corresponding alpha-alkyltryptamines are provided as examples.


Graphite catalyzed reduction of aromatic and aliphatic nitro compounds with hydrazine hydrate.    
Han, Byung Hee; Shin, Dae Hyun; Cho, Sung Yun.  
Tetrahedron Lett.  (1985),  26(50),  6233-4. 
Abstract
RC6H4NO2 (R = H, o-Me, m-Me, p-Me, o-MeO, p-MeO, o-HO, p-HO, m-HO2C, p-H2N, p-HOCH2CH2S, o-MeCH2CH2O, p-MeCH2CH2O, 4-PhO), 6- and 8-nitroquinoline, and 1-nitronaphthalene were reduced to amino compds. in 85-98% yields with graphite and H2NNH2.H2O.


Reductions with hydrazine hydrate catalyzed by Raney nickel. I. Aromatic nitro compounds to amines.    
Balcom, D.; Furst, Arthur.   
J. Am. Chem. Soc.  (1953),  75  4334. 
Abstract
With the addn. of a small amt. of Raney Ni catalyst, N2H4.H2O will selectively reduce an aromatic nitro group to an amine at room or steam bath temp. in yields of 80-99%.  Other functional groups are not affected.  A large amt. of solvent alc. is necessary.  No reduction takes place even after 18 hrs. if the catalyst is not added.  Thus were prepd. the following: p-H2NC6H4OPh, p-H2NC6H4CH:CHCO2H, m-H2NC6H4COPh, 2-MeC6H4C6H4NH4-4, 4-H2NC6H4OC6-H4NH4-4.


The reduction of nitriles to aldehydes by means of hydrazine and Raney nickel.    
Pietra, Silvio; Trinchera, Carlo.   
Gazz. chim. ital.  (1955),  85  1705-9. 
Abstract
Partial reduction of nitriles has been restricted to a few nitriles, for none of the 3 methods of reduction reported, viz., by SnCl2, catalytic hydrogenation, and LiAlH4, are of general application.  The new method of P. and T. employs N2H4.H2O (I) with a hydrogenation catalyst, and is an adaptation of that used by P. for prepg. amines from NO2 compds. (cf. Ann. chim. (Rome) 45, 850 (1955)).  Reduction gives the hydrazone and the azine, which are hydrolyzed to the aldehyde.  Only aromatic nitriles are reported in the present paper, and high yields were obtained with nitriles for which the SnCl2 method of Stephen (C.A. 19, 3261) gives very low yields.  The highest yields are obtained at relatively low temps., viz., 35-55, with a small proportion of catalyst, and with a proportion of I much greater than that for the reaction 2RCN + 3I 2RCH:NNH2 + N2 + 2NH3.  These conditions are most favorable because I is decompd. by Raney Ni (II).  The reactions are probably: RCN H2O RCH:NH I RCH:NNH2, or else with the initial formation of RC(:NH)NHNH2 compd., formed by nucleophilic addn. of I to the nitrile.  PhCN (1 g.) in 4 cc. anhyd. EtOH, 3 cc. I, and 50 mg. II kept 24 hrs. at 35 with const. agitation, filtered, 20 cc. H2O added, the mixt. acidified (Congo red) with dil. HCl, agitated several min., filtered, and the residue purified by EtOH gives 87% (PhCH:N)2 (III), m. 93.  o-MeC6H4CN (1 g.), 5 cc. anhyd. EtOH, 3 cc. I, and 50 mg. II heated 18 hrs. at 55 and treated as before give 78% (o-MeC6H4CH:N)2 (IV), yellow, m. 100.  Likewise m-MeC6H4CN, after 24 hrs. at 35 gives 82% (m-MeC6H4CH:N)2 (V), yellow, m. 74, and p-MeC6H4CN, after 40 hrs. at 35 gives 82% (p-MeC6H4CH:N)2 (VI), yellow, m. 154-4.5.  1-C10H7CN (1 g.), 4 cc. anhyd. EtOH, 3 cc. I, and 50 mg. II, allowed to react 18 hrs. at 55, filtered, the II washed with EtOH, 0.5 vol. H2O added to the filtrate, the mixt. allowd to stand several hrs., and the ppt. crystd. from benzine gives the hydrazone, 1-C10H7CH:NNH2 (VII), m. 92-3.  The aq. alc. mother liquor, acidified (Congo red) with concd. HCl, allowed to stand several min., 10 cc. 10% EtOH added, and the pptd. purified by EtOH give (1-C10H7CH:N)2 (VIII), m. 154-5.  The total yield of VII and VIII (calcd. as VIII) is 69%.  2-C10H7CN (1 g.), 15 cc. anhyd. EtOH, 3 cc. I, and 150 mg. II, heated 18 hrs. at 55, filtered at 55, the residue washed with EtOH, then boiling EtOH, the filtrate allowed to stand, and the ppt. purified by benzine gives 2-C10H7CH:NNH2 (IX), m. 147.  The aq. mother liquor, acidified, allowed to stand, and the ppt. purified by AcOH gives 0.12 g. (2-C10H7CH:N)2 (X), yellow, m. 231.  The total yield of IX and X (calcd. as X) is 59%.  The aldehydes were obtained by passing steam into a suspension of the azine or hydrazone in dil. H2SO4.  III, IV, and V are hydrolyzed by dil. H2SO4; VI and X do not either fuse or dissolve in boiling dil. H2SO4, so they are treated with 50-60% H2SO4 and steam is passed through these solns. 


Reduction of nitro derivatives with hydrazine and palladium.
Pietra, Silvo.   
Ann. chim. (Rome)  (1955),  45  850-3. 
Abstract
Aromatic nitro compds. are reduced to the corresponding amines in good yield by refluxing with excess N2H4.H2O (I) and 5% Pd-C catalyst (II).  PhNO2 (2.46 g.) in 10 ml. EtOH contg. 3 ml. I heated to 40-50, 70 mg. II added with the reaction moderated by cooling, refluxing resumed for a few min. until no more gas is evolved, the C filtered off, and the filtrate dild. with H2O and extd. with Et2O yields 95% PhNH2.  Other reductions are effected similarly, except as specified (yields in parentheses): o- and m-MeC6H4NO2, treated 30 min. (95%); p-MeC6H4NO2, product ppts. on diln. of the reaction mixt. (82%); 1-C10H7NO2 (1.73 g.) in 13 ml. EtOH with 80 mg. II, refluxed 1 hr., product ppts. (88%); nitrofluorescein (1 g.) with 25 mg. II, product ppts. (85%); p-O2NC6H4CO2H (1.67 g.) in 7 ml. H2O with 2 ml. I and 40 mg. II (no EtOH), filtrate acidified with AcOH to ppt. product (84%); o-, m-, and p-O2NC6H4NH2, product isolated from the filtered alc. soln. by fractional distn. in vacuo under N (88, 95, 95%). 


Reduction of aromatic nitro compounds with hydrazine catalyzed by activated zinc-copper.    
Han, Byung Hee; Shin, Dae Hyun; Lee, Hyun Ro; Ro, Bong Ho.
Bull. Korean Chem. Soc.  (1989),  10(3),  315-16. 
Abstract
The title catalyst (I), prepd. by treating CuSO4 with Zn in H2O, gave high yields (generally 86-95%) of arom. amines in the title redn.  Thus, 2-, 3- and 4-MeC6H4NO2 were treated with H2NNH2 in EtOH in the presence of I to give 90, 90 and 92% 2-, 3- and 4-MeC6H4NH2 resp.
Full text
http://www.kcsnet.or.kr/publi/bul/bu89n3/315.pdf


Montmorillonite-catalyzed reduction of nitroarenes with hydrazine.
Han, Byung Hee; Jang, Dong Gyu.
Tetrahedron Lett.  (1990),  31(8),  1181-2.
Abstract
Arom. nitro compds. were readily reduced to the corresponding amino compds. in good yields with N2H4 in the presence of montmorillonite K-10.  E.g., 6-nitroquinoline gave 96% 6-aminoquinoline.


Reduction of nitriles to amines by catalytic transfer hydrogenation.
You, Qidong; Zhou, Houyuan; Wang, Qizhuo;
Huaxue Xuebao  (1993),  51(1),  83-9. Journal  written in Chinese.   
Abstract
A simple and convenient method for redn. of nitriles to amines was reported.  In the presence of sodium hydroxide, nickel chloride (NiCl2.6H2O) was reduced by hydrazine hydrate to deposit active nickel metal which, in turn, catalyzed the hydrogen transfer from hydrazine hydrate to nitriles, thus affording amines in moderate yields (35 .apprx. 82%).  But the poor yields of amines (12 .apprx. 17%) from a.b-unsatd. nitriles were obtained.


Reductive amination of ketones and aldehydes with hydrazine using borohydride exchange resin (BER)-nickel acetate in methanol.    
Nah, Jae Hou; Kim, Suk Youn; Yoon, Nung Min.    
Bull. Korean Chem. Soc.  (1998),  19(2),  269-270.  Journal  written in English.
Abstract
Good yields of primary amines were obtained in the title reaction.  E.g., cyclohexylamine was obtained in 88% yield from cyclohexanone.
Full text avail. here
http://www.kcsnet.or.kr/publi/bul/bu98n2/269.pdf

Activated Molybdenum Promoted Reduction of Nitroarenes with Hydrazine monohydrate
http://www.kcsnet.or.kr/publi/bul/bu94n11/1012.pdf


Reduction of Aromatic Nitro Compounds with Hydrazine in the Presence of Sodium Nitrate-Carbon
http://www.kcsnet.or.kr/publi/bul/bu91n6/709.pdf


Organic Sonochemistry. Ultrasonic Acceleration of the Reduction of Aromatic Nitro Compounds with Hydrazine-Iron in the Presence of Activated Carbon
http://www.kcsnet.or.kr/publi/bul/bu85n5/320.pdf


Organic Sonochemistry. The Effects of Sonic Waves on the Reduction of Aromatic Nitro Groups Using Sulfur-Hydrazine
http://www.kcsnet.or.kr/publi/dh/dh91n2/179.pdf


The Effects of Sonic Waves on the Reduction of Nitrobenzene Using Hydrazine, Zinc and Activated Carbon
http://www.kcsnet.or.kr/publi/dh/dh88n6/607.pdf


The Effects of Sonic Waves on the Reduction of Aromatic Nitro Groups Using Iron, Hydrazine Hydrate and Activated Carbon
http://www.kcsnet.or.kr/publi/dh/dh86n1/105.pdf


Organic Sonochemistry. Ultrasonically Accelerated Hydrogenation of Olefins Using Palladium-Hydrazine
http://www.kcsnet.or.kr/publi/bul/bu85n4/247.pdf


Solvent-free reduction of aromatic nitro compounds with alumina-supported hydrazine under microwave irradiation.
Vass, A.; Dudas, J.; Toth, J.; Varma, R. S.  
Tetrahedron Lett.  (2001),  42(32),  5347-5349.
Abstract
Arom. nitro compds. are readily reduced to the corresponding amino compds. in good yield with hydrazine hydrate supported on alumina in the presence of FeCl36H2O, Fe(III) oxide hydroxide or Fe(III) oxides.


Reductive amination of 1-[3-(2-alkylbenzofuranyl)]-2-phenylethanones. Synthesis of 1-[3-(2-alkylbenzofuranyl)-2-phenylethylamines.
Kwiecien, Halina; Bogdanska, Irena.
Heterocycles  (2001),  55(6),  1113-1119. 
Abstract
1-[3-(2-Alkylbenzofuranyl)]-2-phenylethylamines I (R = Et, Bu, R1 = MeO, H, X = H, Y = NH2) were prepd. by redn. of the corresponding 1-[3-(2-alkylbenzofuranyl)]-2-phenylethanone azines with amalgamated aluminum.  Two isomeric azines were sepd. from products of reaction of 1-[3-(2-alkylbenzofuranyl)]-2-phenylethanones I (XY = O) with hydrazine hydrate in ethanol soln.  On the other hand, instead of the desired amine, an aziridine deriv. was obtained by redn. of the mixt. of (Z)- and (E)-1-[3-(2-butylbenzofuranyl)-2-(4-methoxyphenyl)]ethanone oximes with lithium aluminum hydride.  The redn. of 1-[3-(2-butylbenzofuranyl)]-2-phenylethanone hydrazone with aluminum lead up to the corresponding imine.

Do Your Part To Win The War
 
 
 
 
    foxy2
(Distinctive Doe)
12-03-01 03:45
No 243554
      Re: Hydrazine Info Ect.  Bookmark   

A Consideration of Hydrazine Syntheses
Hac Ki Lee
Journal of the Korean Chemical Society
Volume 5, Number 1 (1961)

It is important to study hydrazine because of the development of new uses for its derivatives. The Rasching method is the only satisfactory one for synthesizing hydrazine; it involves the oxidation of ammonia by sodium hypochlorite in the presence of some such catalyst as gelatin. Calcium hypochlorite was substituted for the sodium hypochlorite particularly in this work, applying agar-agar as catalyst. The results of the experiments are as follow:
1. The yield is proportional to the mole-ratio of ammonia to available chlorine in calcium hypochlorite and about 60% is obtained when the ratio is 20.
2. Agar-agar can be used as a catalyst and its proper concentration in the solution is 0.005%.
3. Proper concentration of available chlorine in the reaction solution is 0.23 mole/l.
4. The most effective condition for the reaction is a temperature of 6065. maintained for 2025 min.
5. The reaction takes place equally well in either an open or closed container.
6. When calcium hypochlorite is applied in place of sodium hypochlorite, the yield of hydrazine is increased as much as 17%.
7. The yield of hydrazine is decreased by eliminating the suspension of Ca(OH)>2 which results from the use of calcium hypochlorite.
8. When Ca(OH)2 is added to Rasching process, the yield of hydrazine is raised normally.
9. The fact that some metal ions, such as Cu++, inhibit the formation of hydrazine was proved.
10. The suspension of Ca(OH)2 acted as a remarkable adsorbent for Cu++ like gelatin.
The suspension of Ca(OH)2 which results from the use of calcium hypochlorite acts as a catalyst, absorbing metal ions, to increase the yield of hydrazine. So I think that calcium hypochlorite is a more efficient oxidant than sodium hypochlorite in hydrazine syntheses.

http://www.kcsnet.or.kr/publi/dh/dh61n1/dh61n1.html#dh61n1-1

Do Your Part To Win The War
 
 
 
 
    uemura
(Hive Bee)
12-03-01 04:15
No 243567
      Re: What to do with Hydrazine  Bookmark   

foxy,
again very good stuff. Any indication somehwere that the Urushibara nickel could bee used instead of Raney nickel?

Carpe Diem
 
 
 
 
    foxy2
(Distinctive Doe)
12-03-01 04:34
No 243575
      Re: What to do with Hydrazine  Bookmark   

No mention of Urushibara, only my wishful thinking.
Although one reduction used NiCl2 that was reduced to nickel powder by the hydrazine(not the best results tho)  I think Urushibara produced with NaOH activation is pretty active, probably similar to Raney since Raney is also made with NaOH.

Do Your Part To Win The War
 
 
 
 
    Agent_Smith
(Hive Bee)
12-04-01 11:28
No 244133
      Re: What to do with Hydrazine  Bookmark   

Can't you blow stuff up... like really well... with hydrazine

blah blah blah something clever blah blah blah, email at dateline@nbc.com
 
 
 
 
    Rhodium
(Chief Bee)
12-04-01 12:07
No 244142
      Re: What to do with Hydrazine  Bookmark   

Yes, anhydrous hydrazine mixed with something with high oxygen content is a high explosive. Hydrazine/ammonium nitrate mixtures are called Astrolites, and are among the most powerful explosives there is.
 
 
 
 
    PrimoPyro
(Hive Addict)
12-04-01 16:56
No 244243
      Re: What to do with Hydrazine  Bookmark   

Hydrazinium Perchlorate is used as a rocket fuel.

So is a mixture of hydrazine hydrate and methanol with hydrogen peroxide.

A two-part liquid fuel is used on most U.S. Space probes: Hydrazine in one, and dinitrogen tetroxide in the other.

All of these provide enormous power per weight, and are wonderful propellents/explosives.

ALL ARE ALSO INSANELY UNSTABLE IN AMBIENT CONDITIONS! DO NOT FUCK WITH THESE THINGS!

                                                 PrimoPyro


Vivent Longtemps la Ruche! STRIKE For President!
 
 
 
 
    terbium
(Old P2P Cook)
12-04-01 19:40
No 244323
      Re: What to do with Hydrazine  Bookmark   

Hydrazinium Perchlorate is used as a rocket fuel.
It has been evaluated as a rocket fuel. I would be surprised if it has ever been used. It is far to easy to detonate. A chemist I once worked with was missing several fingers from the explosion of a small amount of hydrazine perchlorate. He was holding and stirring a small beaker containing a solution of hydrazine perchlorate when it exploded. The thinking was that the hydrazine prechlorate had started to crystallize from solution and he perhaps crushed a small crystal with the stirring rod thus causing the explosion.

The Space Shuttle Solid Rocket Booster uses ammonium perchlorate as the propellant. I believe that there was a huge explosion in Nevada some years back when the company that made ammonium perchlorate blew up.
 
 
 
 
    PrimoPyro
(Hive Addict)
12-04-01 19:49
No 244326
      Re: What to do with Hydrazine  Bookmark   

I have the video of that facility blowing up. It was taken from a highrise about a mile away or so. the workers videotaping it started the tape after the first explosion, and captured a total of four more, for a total of five huge explosions from this facility. It was manufacturing ammonium perchlorate in large amounts. Amazing....

And Im sorry about your friend. Ive never messed with hydrazinium anything, as Id be too scared to be near it w/o body armor.

They have used it in experimental rocketry for certain (USA) along with many many more dangerous propellants than that. Some things are very dangerous compounds that they test. i.e. nitronium perchlorate and such. I have a great book on propellant chemistry. Wonderful read.

                                                    PrimoPyro

Vivent Longtemps la Ruche! STRIKE For President!
 
 
 
 
    Osmium
(Stoni's sexual toy)
12-05-01 06:01
No 244464
      Re: What to do with Hydrazine  Bookmark   

As far as I remember it's UDMH (unsymmetrical dimethyl hydrazine) which is used for rockets.
 
 
 
 
    foxy2
(Distinctive Doe)
12-05-01 08:07
No 244490
      Re: What to do with Hydrazine  Bookmark   

Most of these synths use Hydrazine Hydrate which is much much safer than anhydrous hydrazine or hydrazine salts

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