GB594453A - Improvements in or relating to organic derivatives of hydrazine - Google Patents
Improvements in or relating to organic derivatives of hydrazineInfo
- Publication number
- GB594453A GB594453A GB222943A GB222943A GB594453A GB 594453 A GB594453 A GB 594453A GB 222943 A GB222943 A GB 222943A GB 222943 A GB222943 A GB 222943A GB 594453 A GB594453 A GB 594453A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrazine
- aliphatic
- groups
- benzaldehyde
- mono
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000002429 hydrazines Chemical class 0.000 title 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract 23
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 8
- 125000001931 aliphatic group Chemical group 0.000 abstract 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 7
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 abstract 6
- -1 polymethylene Polymers 0.000 abstract 5
- 229940095076 benzaldehyde Drugs 0.000 abstract 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 4
- 239000002253 acid Substances 0.000 abstract 3
- 239000004202 carbamide Substances 0.000 abstract 3
- 229910052799 carbon Inorganic materials 0.000 abstract 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 3
- 239000000047 product Substances 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- 125000004429 atoms Chemical group 0.000 abstract 2
- 150000003935 benzaldehydes Chemical class 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 125000004432 carbon atoms Chemical group C* 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 230000000875 corresponding Effects 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 238000004821 distillation Methods 0.000 abstract 2
- 239000000706 filtrate Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 125000004430 oxygen atoms Chemical group O* 0.000 abstract 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 abstract 1
- QELWCZINFNYFIV-UHFFFAOYSA-N 6-hydrazinylhexylhydrazine Chemical compound NNCCCCCCNN QELWCZINFNYFIV-UHFFFAOYSA-N 0.000 abstract 1
- 229960000583 Acetic Acid Drugs 0.000 abstract 1
- LQTRJZAUZSMZRC-UHFFFAOYSA-N Cl.Cl.N(N)CCCCCCNN Chemical compound Cl.Cl.N(N)CCCCCCNN LQTRJZAUZSMZRC-UHFFFAOYSA-N 0.000 abstract 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N Monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 abstract 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 abstract 1
- BXNHTSHTPBPRFX-UHFFFAOYSA-M Potassium nitrite Chemical compound [K+].[O-]N=O BXNHTSHTPBPRFX-UHFFFAOYSA-M 0.000 abstract 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N Putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 abstract 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M Sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000010533 azeotropic distillation Methods 0.000 abstract 1
- ATVOBBDPMHUVQY-UHFFFAOYSA-N benzaldehyde;hydrazine Chemical class NN.O=CC1=CC=CC=C1 ATVOBBDPMHUVQY-UHFFFAOYSA-N 0.000 abstract 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 125000006267 biphenyl group Chemical group 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 abstract 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 238000001640 fractional crystallisation Methods 0.000 abstract 1
- 238000004508 fractional distillation Methods 0.000 abstract 1
- 239000012362 glacial acetic acid Substances 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 230000003301 hydrolyzing Effects 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 abstract 1
- 229940067157 phenylhydrazine Drugs 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 239000004304 potassium nitrite Substances 0.000 abstract 1
- 235000010289 potassium nitrite Nutrition 0.000 abstract 1
- 229940064218 potassium nitrite Drugs 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Aliphatic dihydrazines containing two hydrazino groups or mono-alkyl or mono-aryl-substituted hydrazino groups each of which is attached to a different methylene, or mono-alkyl substituted methylene group, are prepared by heating an aliphatic dihalide in which the two halogen atoms are attached to different methylene or mono-alkyl-substituted methylene groups with hydrazine or a mono-alkyl or mono-aryl derivative of hydrazine, or by reducing the dinitroso derivative of an aliphatic diurea by means of zinc and an aliphatic acid and hydrolysing the product. The methylene or substituted methylene groups are preferably linked by a carbon atom or a chain of carbon atoms, but they may be linked by an atom other than carbon or by a chain which includes one or more atoms other than carbon, e.g. an oxygen atom. It is preferable to heat a solution of the aliphatic dihalide and the hydrazine in a common solvent, e.g. an aqueous lower aliphatic alcohol such as methanol, ethanol or isopropanol. Considerably more hydrazine than theoretical, e.g. from 6 to 24 molecular proportions of hydrazine for each molecular proportion of the dihalide is preferably employed. The unreacted hydrazine is removed from the products of reaction by distillation under reduced pressure and excess aqueous hydrochloric acid may then be added to the residue to convert any remaining hydrazine to its dihydrochloride. The mixture of dihydrochlorides may then be separated by fractional crystallization from methanol or ethanol. The residue remaining after removing unreacted hydrazine may also be dissolved in alcohol containing a little water and a strong base added so as to combine with all the chlorine in the solution. The free aliphatic dihydrazine so formed may be isolated by fractional distillation under low pressure. The dihydrazines may also be isolated in the form of their sulphates or by treating the mixture of dihydrochlorides obtained as above with water and benzaldehyde in the cold when the hydrazine benzaldehyde derivative is precipitated while on allowing the filtrate to stand the dihydrazine benzaldehyde derivative separates out. Unsubstituted alkylene dichlorides react with methyl hydrazine to give polymethylene dimethyl - di - hydrazines of formula: H2N.N(CH3).(CH2)nN(CH3)NH2, ethyl hydrazine gives the corresponding ethyl derivative; phenyl hydrazine, however, gives polymethylene diphenyl dihydrazines of formula: C6H5.NH.NH.(CH2)nNH.NH.C6H5, n in each formula being an integer greater than 1. Aliphatic diamines may be used as starting material by converting them into the corresponding di-ureas by reaction with a metal cyanate, e.g. sodium cyanate, and an acid. The diamines may also be heated with urea, preferably in excess and at 130-150 DEG C., to form the di-ureas. The latter may be converted into their di-nitroso derivatives by the action of a nitrite, preferably sodium or potassium nitrite in the presence of an acid, especially glacial acetic acid, or by treatment with nitrous fumes. The reduction of the di-nitroso compounds to the disemicarbazides is preferably conducted at 0-20 DEG C. Examples of other aliphatic dihydrazines are compounds containing in the chain an oxygen atom, e.g. 2.21-dihydrazino diethyl ether which may be made from 2 : 21-dichloro diethyl ether by the above method. In examples: hexamethylene dihydrazine dihydrochloride is produced by heating hydrazine hydrate or hydrazine in methanol or ethanol with 1 : 6-dichlorohexane, the unchanged hydrazine is distilled off and any remaining hydrazine precipitated as the dihydrochloride by adding hydrochloric acid or separated by means of benzaldehyde as above, in the latter case the benzaldehyde derivative of hexamethylene dihydrazine is finally steam distilled from dilute hydrochloric acid to decompose it and remove the benzaldehyde. Free hexamethylene dihydrazine is obtained by refluxing hydrazine hydrate and 1 : 6-dichlorohexane in methanol, removing some unchanged hydrazine by azeotropic distillation with toluene, adding potassium hydroxide with fresh toluene, continuing the distillation, removing the precipitated potassium chloride and finally distilling the filtrate. In another example, hexamethylene dihydrochloride is obtained by heating hexamethylene diamine and urea at 130-140 DEG C. to form the di-urea, the latter being converted to the dinitroso compound which is then reduced as above and the product hydrolysed with concentrated hydrochloric acid and separated by means of benzaldehyde. 1 : 4-Dichlorobutane may be used instead of the 1 : 6-dichlorohexane and tetramethylene diamine in place of the hexamethylene diamine. 1 : 5-Dichlorpentane is also specified as a starting material. According to the Provisional Specification, the residue linking the hydrazino groups may contain one or more aromatic or heterocyclic rings which may form part of the chain linking the hydrazino groups, whether or not they are directly attached to a hydrazino group or may be present as side groups. It is also stated that substituents on the hydrazino groups may be aralkyl groups, e.g. benzyl, or acyl groups, e.g. formyl, acetyl, benzoyl, and may be attached to either nitrogen atom. Additional starting materials specified are trimethylene-, enneamethylene- and p-benzylene-di-ureas.
Publications (1)
Publication Number | Publication Date |
---|---|
GB594453A true GB594453A (en) | 1947-11-12 |
Family
ID=1627202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB222943A Expired GB594453A (en) | 1943-02-10 | Improvements in or relating to organic derivatives of hydrazine |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB594453A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3102144A (en) * | 1954-09-15 | 1963-08-27 | Fmc Corp | Methylated derivatives of hydrazine |
CN110452133A (en) * | 2019-08-08 | 2019-11-15 | 贵州理工学院 | A kind of preparation method of diazanyl phthalic acid methyl ester derivative |
CN113955727A (en) * | 2021-11-08 | 2022-01-21 | 东力(南通)化工有限公司 | Method for treating redundant waste salt in methyl hydrazine production process |
CN115466197A (en) * | 2022-09-14 | 2022-12-13 | 浙江新码生物医药有限公司 | Method for synthesizing acethydrazide |
-
1943
- 1943-02-10 GB GB222943A patent/GB594453A/en not_active Expired
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3102144A (en) * | 1954-09-15 | 1963-08-27 | Fmc Corp | Methylated derivatives of hydrazine |
CN110452133A (en) * | 2019-08-08 | 2019-11-15 | 贵州理工学院 | A kind of preparation method of diazanyl phthalic acid methyl ester derivative |
CN113955727A (en) * | 2021-11-08 | 2022-01-21 | 东力(南通)化工有限公司 | Method for treating redundant waste salt in methyl hydrazine production process |
CN115466197A (en) * | 2022-09-14 | 2022-12-13 | 浙江新码生物医药有限公司 | Method for synthesizing acethydrazide |
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