A process for producing alicyclic hydrazine derivatives.

Abstract: The present invention relates to a process for producing alicyclic hydrazine derivatives, tetrahydropyridazine and hexahydropyridazine which are useful as intermediate starting materials such as medicines and agricultural chemicals. Especially, the present invention provides; a process for producing an alicyclic hydrazine derivative or its hydrohalogenic acid salt, which comprises reacting a hydrazine hydrohalogenic acid salt with a doil compound or an alicyclic ether compound in the presence of an excessive inorganic acid existing in a free form or in the form of an acid addition salt; a process for producing tetrahydropyridazine from 1-aminopyrrolidine, which comprises oxidizing 1-aminopyrrolidine with an oxidizing agent to form tetrahydropyridazine; and a process for producing hexahydropyridazine, which comprises oxidizing 1-aminopyrrolidine with an oxidizing agent, synthesizing tetrahydropyridazine, and thereafter, hydrogenating the tetrahydropyridazine in the presence of a base.

Description: The present invention relates to a process for producing alicyclic hydrazine derivatives, which are useful as intermediate starting materials for producing medicines and agricultural chemicals. The present inventors proposed a method for producing tert-butylhydrazine hydrohalogenic acid salt by reacting hydrazine hydrohalogenic acid salt and tert-butanol which are industrially or economically advantageous starting materials (Japanese Patent Publication No. 48823/1986). However, it has not yet been known that a difunctional alcohol (diol) or an alicyclic ether compound reacts with a hydrazine hydrohalogenic acid salt to give an alicyclic hydrazine derivative hydrohalogenic acid salt. As a method for producing an alicyclic hydrazine derivative or its hydrohalogenic acid salt, there are known a method of reacting an alkyl dihalide with hydrazine hydrate [USSR Pat. 87-4337106], [J. Am.Chem. Soc. 88 , 3959-3963 (1966)] (prior art 1), and a method of synthesizing alicyclic hydrazine by using an alicyclic amine as a starting material [U. S. Patent 3,317,607] (prior art 2). However, the prior art 1 relating to a method of producing an alicyclic hydrazine derivative or its hydrohalogenic acid salt has a problem that an economically expensive dihalogenobutane is required as a starting material. Furthermore, the prior art 2 is a general method of synthesizing alicyclic hydrazine, but the stability and toxicity of the nitroso body which is an intermediate pose a problem. The present invention overcomes the defects of the conventional techniques, and provides a method of producing an alicyclic hydrazine derivative or its hydrohalogenic acid salt industrially and economically advantageously from an inexpensive starting material which is easy to handle, namely a diol compound or an alicyclic ether compound. The present invention therfore provides a method for producing an alicyclic hydrazine derivative and/or its hydrohalogenide which comprises reacting a hydrazine hydrohalogenic acid and/or a salt thereof with a diol compound and/or an alicyclic ether compound in the presence of excess inorganic acid and/or a salt thereof. The reaction of the present invention, may be continued to provide a method for producing hexahydropyridazine; the extended method therefore comprises reacting hydrazine hydrohalogenic acid salt with butanediol or tetetrahydrofuran to synthesize 1-aminopyrrolidine, and then oxidizing 1-aminopyrrolidine with an oxidizing agent to synthesize tetrahydropyridazine, and thereafter hydrogenating the tetrahydropyridazine in the presence of a base. In a preferred embodiment of the present invention, it is desired that 1. the hydrazine hydrohalogenic acid salt be a hydrazine hydromonohalogenic acid salt expressed by the formula (1) NH 2 NH 2 ·HX wherein X represents a halogen atom; 2. the diol compound be a diol compound expressed by the following formula (2) HO-(CH 2 ) m -A-(CH 2 ) n -OH wherein A represents an oxygen atom, a methylene group or an ethylidene group, and m and n are integers of 1 to 3; 3. the alicyclic ether compound be an alicyclic ether compound shown by the formula (3) wherein r is an integer of 4 or 5; 4. the alicyclic hydrazine derivative be an alicyclic hydrazine derivative expressed by the formula (4) wherein A represents an oxygen atom, a methylene group or an ethylidene group, and m and n are integers of 1 to 3, or expressed by the formula (5) wherein p is an integer of 3 or 4; 5. the excessive inorganic acid be a hydrohalogenic acid or its salt; 6. the excess inorganic acid be present in the form of a hydrazine hydrodihalogenic acid or its salt; and 7. the reaction be carried out at a temperature of 100 to 150°C under an elevated pressure while the mole ratio of the diol compound or the alicyclic ether compound:hydrazine hydromonohalogenic acid salt:excess inorganic acid is 1:1-10:0.2-3. The reaction solution obtained by the above method is concentrated, and an alcohol solvent, etc. is added. The unreacted hydrazine hydrohalogenic acid salt precipitated as crystals are removed in a customary manner. Then, the separated mother liquor is subjected to an ordinary method such as dilution or cooling, whereby an alicyclic. hydrazine derivative hydrohalogenic acid salt precipitated as crystals can be separated and recovered. Furthermore, the above separated mother liquor is neutralized with a base, and distilled to give an alicyclic hydrazine derivative. In the present invention, the diol compound or the alicyclic ether compound is reacted with the hydrazine hydrohalogenic acid salt in the presence of an excess of inorganic acid to give an alicyclic hydrazine derivative at once. In this regard, the reaction of the present invention is novel and peculiar. The diol compound or the alicyclic ether compound, together with the hydrazine hydrohalogenic acid salt, is a starting material which is easily available and cheap. In addition, since the handlability of these materials is easy during the reaction, the invention can provide the alicyclic hydrazine derivative or its hydrohalogenic acid salt industrially advantageously. The excess of inorganic acid may be present in a free form or in the form of an acid addition salt. Hydrohalogenic acids are preferred as the inorganic acid. In this case, the hydrohalogenic acids may exist in the form of hydrazine hydrohalogenic acid. As the hydrohalogenic acids, hydrochloric acid and hydrobromic acid are preferred. As the hydrazine hydrohalogenic acid salt hydrochloride salt and hydrobromide salt may be used. The hydrochloride salt is preferred. The hydrazine hydrohalogenic acid salt shown in the formula (1), namely hydrazine hydromonohalogenic acid salt, is preferred. The hydrazine hydrohalogenic acid salt may be relatively pure, or may contain an impurity. For example, the hydrazine hydrohalogenic acid salt recovered from the mother liquor may be repeatedly used in the reaction. Of course, the hydrazine hydrodihalogenic acid salt used may be used as a starting material for hydrazine. The diol compound may be any compound which is an aliphatic compound having two hydroxyl groups. The number of carbons in the diol compound may be 3 to 8. The hydroxyl groups may be primary, secondary or tertiary hydroxyl groups, but in respect of the reactability, a primary hydroxyl group is preferred. The skeleton of the diol compound may be a straight chain alkylene group or a branched chain alkylene group. In this alkylene chain, atoms other than carbon, such as an ether oxygen atom, may be interposed. Suitable diol compounds may be those represented by general formula (2). Preferred examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol and diethyleneglycol. In the present invention, alicyclic ether compounds may be used instead of the diol compounds. As the alicyclic ether compounds, compounds having 4 to 5 carbon atoms and containing at least one ether oxygen atom within the ring are used. Alicyclic ether compounds expressed by general formula (3) are preferred. Particularly preferred examples include tetrahydrofuran and tetrahydropyran. Tetrahydrofuran is most preferred. According to the present invention, the hydrazine hydrohalogenic acid salt is reacted with the diol compound or the alicyclic ether compound in the presence of an excess of inorganic acid to form an alicyclic hydrazine derivative in the form of a hydrohalogenide salt. This overall process encompasses two specific reactions, namely, where one nitrogen atom of the hydrazine is taken into the ring (reaction A), and where two nitrogen atoms of the hydrazine are taken into the ring (reaction 8). These specific reactions are illustrated below. (1) Reaction A When 1,4-butanediol or tetrahydrofuran is reacted with hydrazine hydrohalogenic acid salt in the presence of an inorganic acid. 1-aminopyrrolidine hydrohalogenic acid salt will be formed as shown in the following formula (6). When 1,5-pentanediol or tetrahydropyran is reacted with hydrazine hydrohalogenic acid salt in the presence of an inorganic acid, 1-aminopiperidine hydrohalogenic acid salt will be formed as shown by the formula (7). When 3-methyl-1,5-pentanediol is reacted with hydrazine hydrohalogenic acid salt in the presence of an inorganic acid, 1-amino-4-methylpiperidine hydrohalogenic acid salt will be formed as shown in the formula (8). When 1,6-hexanediol is reacted with a hydrazine hydrohalogenic acid salt in the presence of an inorganic acid, 1-aminohexamethyleneimine hydrohalogenic acid salt will be formed as shown by the formula (9). When diethylene glycol is reacted with a hydrazine hydrohalogenic acid salt in the presence of an inorganic acid, a 4-aminomorpholine hydrohalogenic acid salt will be formed as shown by the formula (10) (2) Reaction B When 1,3-propanediol is reacted with a hydrazine hydrohalogenic acid salt in the presence of an inorganic acid, a pyrazolidine hydrohalogenic acid salt will be formed as shown by the formula (11). As will be described later, when 1,4-butanediol is used as the starting material, it is recognized that hexahydropyridazine is also formed although its yield is low. In the present invention, the mole ratio of the diol compound or alicyclic ether compound: the hydrazine hydromonohalogenic acid salt (H.HX): the excess inorganic acid (HA) is 1:1-10:0.2-3. Preferably, this mole ratio is 1:2-5:1-2. The reaction temperature is preferably 100 to 150°C, more preferably 110 to 140°C. The reaction pressure is preferably normal pressure to 10 Kg/cm 2 G, more preferably about 2 to 8 Kg/cm 2 G. The reaction time differs depending upon the intended alicyclic hydrazine derivative but is about 1 to 30 hours. In the case of reaction A, when the product is a 1-aminopyrrolidine hydrohalogenic acid salt, the reaction time is 3 to 10 hours. Water can be used as the solvent. Industrially, a method will be available in which H.HX, the diol compound or the alicyclic ether compound, and the excess inorganic acid, or H.HX, the diol compound or the alicyclic ether compound and the hydrazine hydrodihalogenic acid salt are simultaneously charged in a reaction vessel and used in the reaction. Another method is to add the diol compound or the alicyclic ether compound, and the inorganic acid to the H.HX aqueous solution prepared from a hydrazine hydrate and a hydrohalogenic acid. In this reaction, to use H.HX in an excess amount to the diol compound or the alicyclic ether compound, H.HX must be separated from the alicyclic hydrazine derivative hydrohalogenic acid salt in order to obtain the alicyclic hydrazine derivative hydrohalogenic acid salt having a high purity. For that purpose, water used as the solvent is concentrated and an alcohol solvent such as methanol is added, and then the H.HX is crystallized and thereafter taken out as crystals. It is then separated from the intended alicyclic hydrazine derivative hydrohalogenic acid salt. When by one operation, H.HX cannot be fully removed from the reaction solution, the separating operation of H.HX may better be repeated several times. The reaction residue from which H.HX has been removed is left to stand at room temperature whereby the alicyclic hydrazine derivative hydrohalogenic acid salt can be isolated as crystals. Furthermore, the isolated crystalline alicyclic hydrazine derivative hydrohalogenic acid salt was neutralized with a base such as sodium hydroxide and precisely distilled to obtain the desired alicyclic hydrazine derivative. The reaction solution after separating H.HX is neutralized with a base such as sodium hydroxide, the resulting inorganic salt was separated by filtration, and the filtrate was precisely distilled whereby the desired alicyclic hydrazine derivative could be isolated. The amounts of by-products at the time of synthesizing the alicyclic hydrazine derivative hydrohalogenic acid salt are small, and the reaction selectivity is high. For example, when 1,4-butanediol is reacted with hydrazine monohydrochloride salt in the presence of hydrochloric acid to produce 1-aminopyrrolidine hydrochloride salt, the by-products are shown in the following formula (12). Based on an analysis of gas chromatography, four by-products and the reaction selectivity are shown. The 1-aminopyrrolidine 1 showed a high selectivity of more than 90%. The structures of these by-products were identified or assumed. Tetrahydropyridazine 2 and hexahydropyridazine 3 were compared and identified by GC with a standard sample. Since the other two by-products had a molecular weight of 140 by GC-MS analysis, they were assumed to be 1,1-bipyrrolidine 4 produced by the reaction of 1-aminopyrrolidine and 1,4-butanediol and also to be octahydropyridazino[1,2-alpyridazine 5 formed by reaction of hexahydropyridazine 3 and 1,4-butanediol. The outline of the reaction mechanism is shown in the following formula (13). Especially. it has been found that 1-aminopyrrolidine hydrochloric acid salt is obtained peculiarly with a high selectivity and in a high yield. The reaction of the invention and the continuation thereof referred to above are shown by the formula (14). The reaction in the first stage has been already mentioned before. By oxidizing 1-aminopyrrolidine with an oxidizing agent, diazene-hydrazone rearrangement occurs to form tetrahydropyridazine. This tetrahydropyridazine is hydrogenated in the presence of a base to form hexahydropyridazine. As explained above, the hydrazine hydrohalogenic acid salt is reacted with the diol compound or the alicyclic ether compound, The 1-aminopyrrolidine hydrohalogenic acid salt obtained by this reaction or 1-aminopyrrolidine hydrohalogenic acid salt solution containing the mother liquor obtained in this reaction may be used as a synthesizing starting material of tetrahydropyridazine. The resulting tetrahydropyridazine may be hydrogenated in the presence of a base to form hexahydropyridazine. The hydrogenating reaction may be preferably carried out by using a noble metal catalyst. It is important that the catalytic hydrogenation reaction be carried out in the presence of a base. The catalytic hydrogenating reaction of tetrahydropyridazine using a noble metal catalyst gives a by-product of 1-aminopyrrolidine which is a starting material for tetrahydropyridazine in addition to hexahydropyridazine as a desired product. The reaction is shown by the following formula (15). As already stated, tetrahydropyridazine is formed by an oxidation reaction of 1-aminopyrrolidine, and its reverse reaction is thought to occur; namely there is thought a reaction mechanism in which 1-aminopyrrolidine is formed as a by-product from tetrahydropyridazine by a reducing reaction. It is thought that the addition of the base will suppress this reverse reaction. The 1-aminopyrrolidine formed as a by-product may be converted to tetrahydropyridazine by oxidizing it with an oxidizing agent, and again used in the reducing reaction. After the solvent is recovered from a reaction solution of hexahydropyridazine obtained by catalytic hydrogenation of tetrahydropyridazine using a noble metal catalyst, the desired hexahydropyridazine can be isolated by precise distillation. According to the present invention, by reacting hydrazine hydrohalogenic acid salt with a diol compound or an alicyclic ether compound in the presence of an excess of an inorganic acid, alicyclic hydrazine derivatives useful as intermediates of medicines or agricultural chemicals may be produced with industrial or economical advantage. Furthermore, according to the present invention, when tetrahydropyridazine is hydrogenated in the presence of a base, the reaction speed can be increased and the reaction time can be shortened drastically, and it is possible to increase the conversion of tetrahydropyridazine to at least 90% and the selectivity to hexahydropyridazine to at least 90%. Moreover, by oxidizing 1-aminopyrrolidine with an oxidizing agent, the conversion of 1-aminopyrrolidine can be increased to at least 90%, and the selectivity to tetrahydropyridazine can be increased to at least about 60% or more. It is excellent that the reaction time can be shortened considerably, and an after-treatment is not necessary. When oxidation is carried out by using an oxidizing agent, the by-product during the production is only pyrrolidine. In addition, since impurities existing in the starting 1-aminopyrrolidine can be decomposed by oxidation, it is extremely convenient. Thus, 1-aminopyrrolidine is synthesized from hydrazine hydrohalogenic acid salt and butane diol or tetrahydrofuran; and by oxidizing 1-aminopyrrolidine with an oxidizing agent tetrahydropyridazine may be formed, and then the tetrahydropyridazine may be hydrogenated by using a noble metal catalyst to produce with industrial and economical advantages hexahydropyridazine which is very useful as an intermediate for agricultural chemicals or medicines. Examples The present invention will be specifically explained by the following Examples, but the present invention is not limited to these Examples. Analysis of alicyclic hydrazine derivatives including 1-aminopyrrolidine, tetrahydropyridazine and hexahydropyridazine has been conducted by gas chromatography, or neutralization titration using hydrochloric acid or sodium hydroxide. The crystals obtained after concentrating the reaction solution, which are obtained by reacting the hydrazine hydrohalogenic acid salt with the diol compound or the alicyclic ether compound, are a mixture of H.HX and H.2HX. Their composition was determined by titration analysis for H.HX. The recovery rate of H.HX is calculated based on a value obtained by subtracting the charge amount of a reaction substrate from the amount corresponding to H.HX. Example 1 Synthesis of 1-aminopyrrolidine hydrochloric acid salt A 1-liter glass autoclave was charged with 226.1 g (3.30 moles) of hydrazine monohydrochloride, 111.4 g (1.10 moles) of concentrated hydrochloric acid, 99.1 g (1.10 moles) of 1,4-butanediol and 330.0 g of H 2 O. With stirring, they were reacted at 140°C and under 2.2 to 5.6 Kg/cm 2 G for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 179.9 g of the product as crystals. The mixture had a composition which was determined by titration with 1N-NaOH and contained 77.40 % by weight [139.24 g (2.03 mols), recovery rate 92.27%] of hydrazine monohydrochloride and 20.82 % by weight [37.46 g (1.03 mols), recovery rate 93.29%] of HCl. Methanol (20 g) was added to 162.0 g of the reaction methanol solution concentrated. The mixture was allowed to stand at room temperature to give 79.8 g of white primary crystals of 1-aminopyrrolidine hydrochloric acid salt. (Content: titrated 101.87%, GC 99.66% (0.65 mole) was isolated.) Furthermore, the separated mother liquor was concentrated to give 23.9 g of white secondary crystals of 1-aminopyrrolidine hydrochloric acid salt. (Content: titrated 96.88%. GC 94.53% (0.19 mole) was isolated.) The yield of 1-aminopyrrolidine hydrochloric acid salt crystals was 76.40%. The separated mother liquor contained 58.57 % by weight [14.87g (0.12 mole)] of 1-aminopyrrolidine hydrochloric acid salt remaining therein. The total yield of 1-aminopyrrolidine hydrochloric acid salt was 87.4%. Furthermore, 1,4-butanediol did not remain (GC analysis). Incidentally, the identification of 1-aminopyrrolidine was performed by showing that the holding time of a standard sample of 1-aminopyrrolidine agreed with the holding time of GC and by following NMR/ 1 H-NMR (a mixed solvent comprising DMSO-d 6 and CDCl 3 ) 1.83-2.26 (m, 4H, -CH 2 -) 3.23-3.67 (m, 4H, -CH 2 -) 7.88 (bs, 3H, -NH 2 , HCl) ~ D exchangeable Example 2 Synthesis of 1-aminopyrrolidine hydrochloric acid salt A 1-liter glass autoclave was charged with 150.7 g (2.20 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hydrazine dihydrochloride, 99.1 g (1.10 moles) of 1,4-butanediol, and 401.3 g of H 2 O. With stirring, they were reacted at 140°C for 3 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 183.0 g of crystals. The composition of the mixture was titrated with 1N-NaOH and contained 77.92 % by weight [142.59 g (2.08 mols), recovery rate 94.61%] of hydrazine monohydrochloride and 19.72 % by weight[36.09 g (0.99 mol), recovery rate 89.88%] of HCl. Methanol (20 g) was added to the concentrated reaction solution, and 149.6 g of the methanol solution of the concentrated reaction solution was left to stand at room temperature to isolate 79.7 g of white primary crystals of 1-aminopyrrolidine hydrochloric acid salt, content: titrated 100.43%, GC98.40% (0.65 mole). Furthermore, the separated mother liquor was concentrated to give 21.9 g of white secondary crystals of 1-aminopyrrolidine hydrochloric acid salt, content: titrated 97.03%, GC92.70% (0.17 mole). The yield of 1-aminopyrrolidine hydrochloric acid salt crystals was 74.90%. The separated mother liquor contained 46.70 % by weight [10.09 g (0.082 mole)] of 1-amino-pyrrolidine hydrochloric acid salt remaining therein. The presence of a small amount of 1,4-butanediol was confirmed (GC analysis). The total yield of 1-aminopyrrolidine hydrochloric acid salt was 82.3%. Example 3 Synthesis of 1-aminopyrrolidine hydrochloric acid salt: A 1-liter glass autoclave was charged with 150.7 g (2.20 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hyrazine dihydrochloride, 103.6 g (1.15 moles) of 1,4-butanediol and 401.3 g of H 2 O. With stirring, these substances were reacted at 140°C for 3.5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate white crystals in an amount of 181.2 g. The composititon of the mixture was titrated with 1N-NaOH to give 76.60% by weight [138.80 g (2.03 moles), the recovery rate 94.42%] of hyrazine monohychloride, 21.79 % by weight [39.48 g (1.08 moles), the recovery rate 98.33%] of HCl. The mixture of (hydrazine monohydrochloride + hydrazine dihydrocloride) was separated. The 1-aminopyrrolidine hydrochloric acid salt in 445.7 g of the methanol mother liquor had a content of 28.92% as titrated, 128.90 g (1.05 moles), and the formation rate was 91.42%. Incidentally, 1,4-butanediol did not remain (GC analysis). The reaction selectivity was sought from the GC analysis of the methanol mother liquor. Four by-products existed in addition to 1-aminopyrrolidine. By a GC-MS analysis, one compound was determined to be hexahydropyridazine because it had a molecular weight of 86 and it had the same holding time (GC) as the standard sample. Another compound was determined to be tetrahydropyridazine because it had a molecular weight of 84, and it had the same holding time (GC) as a standard sample. Furthermore, the other two compounds were assumed to be 1,1-bipyrrolidine and octahydropyridazino[1,2-a]pyridazine because both had a molecular weight of 140. The reaction selectivities of the compounds in the methanol mother liquor were 90.17% of 1-aminopyrrolidine, 4.03% of hexahydropyridazine, 0.41% of tetrahydropyrazine, by-products having a molecular weight of 140, 4.72% of 1,1-bipyrrolidine, and 0.67% of octahydropyridazino[1,2-a]pyridazine, and the selective formation of 1-aminopyrrolidine was confirmed. Example 4 Sythesis of 1-aminopyrrolidine hydrochloric acid salt: A 1-liter glass autoclave was charged with 226.1 g (3.30 moles) of hydrazine monohydrochloride, 111.4 g (1.10 moles) of concentrated hydrochloric acid, 99.1 g (1.10 moles) of 1,4-butanediol and 330.0 g of H 2 O. With stirring, these compounds were reacted at 130°C for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to sepatate 179.9 g of white cyrscals. The composition of the mixture was determined by titration with 1N-NaOH and contained hydrazine monohydrochloride 86.54 % by weight, [155.69 g (2.27 moles), the recovery rate 103.18%], and HCl 20.88% by weight, 137.57 g (1.03 moles), the recovery rate 93.57%]. 128.1 g of the reaction concentrated methanol solution was allowed to stand at room temperature to isolate 65.8 g of white primary crystals of 1-aminopyrrolidine hydrochloric acid salt. Content: titrated 99.40%, GC98.58% (0.54 mole). Furthermore, the separated mother liquor was concentrated to give 8.9 g of white secondary crystals of 1-aminopyrrolidine hydrochloric acid salt, content: titrated 93.25%, GC94.36% (0.07 mole). The yield of 1-aminopyrrolidine hydrochloric acid salt crystals was 55.39%. The separated mother liquor contained 55.56 % by weight of 1-aminopyrrolidine hydrochloric acid salt, 18.50 g (0.15 mole) remaining therein. Incidentally, a small amount of 1,4-butanediol was confirmed (GC analysis). The total yield of 1-aminopyrrolidine hydrochloride was 69.1%. Example 5 Synthesis of 1-aminopyrrolidine hydrochloric acid salt: A 1-liter glass autoclave was charged with 226.1 g (3.30 moles) of hydrazine monohydrochloride, 111.4 g (1.10 moles) of concentrated hydrochloric acid, 99.1 g (1.10 moles) of 1,4-butanediol. and 330.0 g of H 2 O. With stirring, the above compounds were reacted at a temperature of 120°C for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 205.0 g of white crystals. The composition of the mixture was titrated with 1N-NaOH to give hydrazine monohydrochloride 80.28 % by weight, 164.57 g (2.40 moles), the recovery rate 109.09%, and HCl 18.29 % by weight, 37.49 g (1.03 moles), the recovery rate 93 .38%. A small amount of methanol was added to 107.6 g of the reaction concentrated solution, and the mixture was left to stand at room temperature to isolate 22.9 g of white primary crystals of 1-aminopyrrolidine hydrochloric acid salt, content: titrated 99.73%, GC 99.13% (0.19 mole). Furthermore, the separated mother liquor was concentrated to obtain 36.5 g of white secondary crystals of 1-aminopyrrolidine hydrochloric acid salt, content: titrated 93.56%, GC95.10% (0.28 mole). The yield of 1-aminopyrrolidine hydrochloric acid salt crystal was 42.30%. The separated mother liquor contained 58.91 % by weight of 1-aminopyrrolidine hydrochloric acid salt [25.33 g (0.21 mole)] remaining therein. Incidentally, a small amount of 1,4-butanediol was confirmed (GC analysis). The total yield of 1-aminopyrrolidine hydrochloride salt was 61.0%. Example 6 Precise distillation of 1-aminopyrrolidine 1-Aminopyrrolidine hydrochloric acid salt white crystals, Example 5, primary crystals 21.0 g (content: titrated 99.73%), secondary crystal 33.2 g (93.56%), Example 4, primary crystals 65.0 g (99.40%), secondary crystals 7.5 g (93.25%), Example 2, primary crystals 40.4 g (100.43%), and secondary crystals 20.5 g (97.03%) were dissolved in methanol, and the solution was neutralized with 60.0 g (1.50 moles) of NaOH. After neutralization, the precipitated sodium chloride was separated to give 207.2 g of a methanol solution of 1-aminopyrrolidine [1-aminopyrrolidine 44.80% by weight, 121.05 g (1.41 moles)]. A portion of this methanol solution was taken, and methanol was added to give 266.2 g (1.38 moles) of a methanol solution of 1-aminopyrrolidine. The above methanol solution was precisely distilled in a distillation tower filled with Helipack. After recovering methanol, 66.8 g (0.77 mole) of 1-aminopyrrolidine [content: 97.56% (GC)] was isolated at a boiling point of 128 to 130°C. The 1-aminopyrrolidine was identified with NMR. 1 H-NMR (CDCl 3 ) 1. 63-2.13 (m, 4H, -CH 2 -) 2. 57-2.96 (m, 4H, -CH 2 -) 3. 27 (bs, 3H, -NH 2 ), ~ D exchangeable Example 7 Synthesis of 1-aminopyrrolidine hydrochloric acid salt A 1-liter glass autoclave was charged with 274.0 g (4.00 moles) of hydrazine monohydrochloride, 105.5 g (1.00 mole) of hydrazine dihydrochloride, 90.1 g (1.00 mole) of 1, 4-butanediol and 364.8 g of H 2 O, and with stirring, these substances were reacted at 140°C for 4 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 301.8 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH to give hydrazine monohydrochloride 86.26% by weight, 260.33 g (3.80 moles), the recovery rate 95.00% and HCl 10.95 % by weight, 33.05 g (0.91 mole), the recovery rate 90.54%. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), 1-aminopyrrolidine hydrochloric acid salt in 310.8 g of the methanol mother liquor was 115.15 g (0.94 mole) [content: titrated 37.05%] and the formation rate was 93.92%. The reaction selectivity in the methanol mother liquor was 91.89% of 1-aminopyrrolidine, 5.54% of hexahydropyridazine, a by-product having a molecular weight of 140, 2.28% of 1,1-bipyrrolidine and 0.29% of octahydropyridazino [1, 2-a]pyridazine, and the selective formation of 1-aminopyrrolidine was confirmed. Incidentally, 1,4-butanediol did not remain (GC analysis). Example 8 Synthesis of 1-aminopyrrolidine hydrochloric acid salt: A 1-liter glass autoclave was charged with 75.4 g (1.10 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hydrazine dihydrochloride, 99.1 g (1.10 moles) of 1,4-butanediol and 401.3 g of H 2 O, and with stirring, the above compounds were reacted at 140°C for 4 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 122.0 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH and contained, 68.09% by weight of hydrazine monohydrochloride [83.07 g (1.21 moles), the recovery rate 110.23%] and 30.69% by weight of HCl [37.44 g (1.03 moles), the recovery rate 93.25%]. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), 1-aminopyrrolidine hydrochloric acid salt in 362.4 g of the methanol mother liquor contained 109.48 g (0.89 mole) [content: titrated 30.21%], and the formation rate was 80.91%. The reaction selectivity in the methanol mother liquor was 88.30% of 1-aminopyrrolidine, 3.13% of hexahydropyridazine, a by-product having a molecular weight of 140, 6.40% of 1,1-bipyrrolidine and 0.83% of octahydropyridazino[1,2-a]pyridazine, and the selective formation of 1-aminopyrrolidine was confirmed. Incidentally, 1, 4-butanediol remained in a small amount (GC analysis). Example 9 Synthesis of 1-aminopyrrolidine hydrochloric acid salt: A 1-liter glass autoclave was charged with 115.5 g (1.10 moles) of hydrazine dihydrochloride, 99.1 g (1.10 moles) of 1,4-butanediol and 401.3 g of H 2 O, and with stirring, the above substances were reacted at 140°C for 3.5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 54.9 g of white crystals. The composition of the mixture was titrated with 1N-NaOH was as follows: hydrazine monohydrochloride 64.21% by weight, 35.25 g (0.51 mole), HCl 33.99% by weight, 18.66 g (0.51 mole). After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), 1-aminopyrrolidine hydrochloric acid salt in 475.2 g of the methanol mother liquor was as follows: content: titrated 13.36%, 63.49 g (0.52 mole), and the formation rate 47.07%. The reaction selectivity in the methanol mother liquor was 81.22% of 1-aminopyrrolidine. 2.34% of hexahydropyridazine, a by-product having a molecular weight of 140, 8.12% of 1,1-bipyrrolidine, and 0.89% of octahydropyridazino[1,2-a]pyridazine. Incidentally, 1,4-butanediol remained in a small amount (GC analysis). Example 10 Synthesis of 1-aminopyrrolidine hydrochloric acid salt by tetrahydrofuran A 1-liter glass autoclave was charged with 150.7 g (2.20 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hydrazine dihydrochloride, 79.3 g (1.10 moles) of tetrahydrofuran and 401.3 g of H 2 O, and with stirring. the above substances were reacted at 140°C for 3.5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 187.6 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH with the following results. Hydrazine monohydrochloride 77.90 % by weight, 146.14 g (2.13 moles), the recovery rate 96.96%, HCl 20.05% by weight, 37.61 g (1.03 moles), and the recovery rate 93.68%. The reaction concentrated solution (152.8 g) was allowed to stand to isolate 79.1 g of white primary crystals of 1-aminopyrrolidine hydrochloric acid salt [content:titrated 99.71% (0.65 mole)]. Furthermore, the separated mother liquor was concentrated to give 22.3 g of white secondary crystals of 1-aminopyrrolidine hydrochloric acid salt, content:titrated 94.79% (0.18 mole). The yield of 1-aminopyrrolidine hydrochloric acid salt crystals was 75.45%. In the separated mother liquor, 74.20 % by weight [17.07 g (0.14 mole)] of 1-aminopyrrolidine hydrochloric acid salt remained. The total yield of 1-aminopyrrolidine was 88.2%. Example 11 Synthesis of 1-aminopyrrolidine hydrobromic acid salt A 200 ml pressure-resistant glass bomb was charged with 101.7 g (0.45 mole) of 50% hydrazine hyrobromide, 25.8 g (0.45 mole) of 47% hydrobromic acid, and 13.5 g (0.15 mole) of 1, 4-butanediol, and the above substances were reacted at 140°C for 3.5 hours. After the reaction, the formation rate of 1-aminopyrrolidine hydrobromide during the reaction was 88.4% (quantitatively analyzed by GC). The selectivity in the reaction solution was 73.61% of 1-aminopyrrolidine hydrobromic acid salt, 5.66% of hexahydropyridazine, a by-product having a molecular weight of 140, 16.13% of 1,1-bipyrrolidine, and 3.50% of octahydropyridazino [1,2-a]pyridazine. Incidentally, 1,4-butanediol did not remain (GC analysis). Example 12 Precise distillation of 1-aminopyrrolidine After synthesizing 1-aminopyrrolidine hydrochloric acid salt, 656.5 g of a 1-aminopyrrolidine hydrochloric acid salt reaction solution [Composition: (1-aminopyrrolidine hydrochloric acid salt + hydrazine monohydrochloride) 83.05 % by weight, 545.22 g (4.45 moles), HCl 2.40 % by weight, 15.76 g (0.43 mole)] remaining after recovering a mixture (of hydrazine monohydrochloride + hydrazine dihydrochloride) was formed. To the above 1-aminopyrrolidine hydrochloric acid salt solution was added 100 g of methanol, and the methanol solution was neutralized with 200.1 g (5.00 moles) of sodium hydroxide. After neutralization, 330.2 g of sodium chloride was separated. Thereafter, 969.6 g of 1-aminopyrrolidine methanol solution [composition: 1-aminopyrrolidine 29.43% by weight, 285.35 g (3.31 moles), hydrazine hydrate 4.90% by weight, 47.56 g (0.95 mole)] was obtained. 912.1 g of 1-aminopyrrolidine methanol neutralized solution [composition: 1-aminopyrrolidine 29.43 % by weight, 268.4 g (3.12 moles), hydrazine hydrate 4.90% by weight, 45.1 g (0.90 mole), methanol 57.78% by weight, 527.0 g, H 2 O 7.86% by weight, 71.7 g] was precisely distilled by using a distillation tower packed with Helipack. After recovering methanol at normal pressure, methanol, water, hydrazine hydrate, and pyrrolidine fractions were removed under reduced pressure, and 99.3% (GC) of 1-aminopyrrolidine was isolated at 70 mmHg and 55 to 62°C. Example 13 Synthesis of 1-aminopiperidine hydrochloric acid salt A 200 ml pressure-resistant glass bomb was charged with 27.4 g (0.40 mole) of hydrazine monohydrochloride, 21.0 g (0.20 mole) of hydrazine dihydrochloride, 20.8 g (0.20 mole) of 1,5-pentanediol and 60.0 g of H 2 O, and by a shaking machine, the above substances were reacted at 140°C for 24 hours. After the reaction, the reaction solution was separated into two layers. After separation, the upper layer and the lower layer were separately treated. By a GC-MS analysis of the upper layer reaction solution, the formation of 5-chloro-1-pentanol as a chlorinated product of 1,5-pentanediol, and 1,5-dichloropentane was ascertained. The lower layer reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 34.4 g of white crystals. The composition of the mixture was titrated with 1N-NaOH to give hydrazine monohydrochloride 84.24% by weight, 28.98 g (0.42 mole), the recovery rate 105.75% and HCl 13.15 % by weight, 4.52 g (0.12 mole), the recovery rate 62.0%. The mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was separated, and 1-aminopiperidine hydrochloric acid salt in 97.3 g of the methanol mother liquor was 14.93% (titrated), 14.53 g (0.11 mole), and the formation rate was 53.2%. 1-Aminopiperidine was identified by GC-MS and the fact that the holding time of GC of the standard sample coincided with the holding time of GC of the product. Incidentally, the reaction selectivity of 1-aminopiperidine was 92.9% (GC). Example 14 Synthesis of 1-aminopiperidine hydrochloric acid salt A 200 ml pressure-resistant glass bomb was charged with 27.4 g (0.40 mole) of hydrazine monohydrochloride, 21.0 g (0.20 mole) of hyrazine dihydrochloride, 17.2 g (0.20 mole) of tetrahydropyran and 60.0 g of H 2 O, and by a shaking machine, the above substances were reacted at 140°C for 24 hours. After the reaction, the reaction solution was separated into two layers. After separating the solution, the upper layer and the lower layer were separately treated. In the upper layer, the formation of 5-chloro-1-pentanol which was a chlorinated product of 1,5-pentanediol, and 1,5-dichloropentane was confirmed. The lower layer reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was recovered to obtain 89.5 g of the reaction concentrated methanol mother liquor. 1-Aminopiperidine hydrochloric acid salt in the methanol mother liquor was 2.75% as titrated [2.46 g (0.07 mole)], the formation rate 33.8%]. Example 15 Synthesis of 1-amino-4-methylpiperidine hydrochloric acid salt A 1-liter glass autoclave was charged with 226.1 g (3.30 moles) of hydrazine monohydrochloride, 111.4 g (1.10 moles) of concentrated hydrochloric acid, 127.8 g (1.10 moles) of 3-methyl-1,5-pentanediol and 400.0 g of H 2 O, and with stirring, the above substances were reacted at 140°C for 24 hours. After the reaction, the reaction solution was separated into two layers. Then, after separation, the upper layer and the lower layer were separately treated. By a GC-MS analysis of the upper layer reaction solution, the formation of 5-chloro-3-methyl-1-pentanol which was a chlorinated product of 3-methyl-1,5-pentanediol and 1,5-dichloro-3-methylpentane was confirmed. The lower layer reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was recovered to give 174.4 g of the reaction concentrated methanol mother liquor. 1-Amino-4-methylpiperidine hydrochloric acid salt in the methanol mother liquor was 8.57% as titrated, 15.20 g (0.10 mole), and the formation rate was 9.2%. Incidentally, 1-amino-4-methylpiperidine was identified by GC-MS. Example 16 Synthesis of 1-aminohexamethyleneimine hydrochloric acid salt A 1-liter glass autoclave was charged with 150.7 g (2.20 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hydrazine dihydrochloride, 130.0 g (1.10 moles) of 1,6-hexanediol and 401.3 g of H 2 O, and with stirring, the above substances were reacted at 140°C for 22 hours. After the reaction, the reaction solution was separated into two layers. Then, after the separation, the upper layer and the lower layer were separately treated. By the GC-MS analysis of the upper layer reaction solution, the formation of 6-chloro-1-hexanol which was a chlorinated product of 1,6-hexanediol, and 1,6-dichlorohexane was confirmed. The lower layer reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride was washed with methanol to separate 134.7 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH to give 79.37% by weight of hydrazine monohydrochloride [106.9 g (1.56 moles), the recovery rate 70.95%], and 18.37% by weight of HCl [24.7 g (0.68 mole), the recovery rate 61.6%]. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), the amount of 1-aminohexamethyleneimine hydrochloric acid salt in the methanol mother liquor was 6.26 g (0.055 mole), and the formation rate was 4.98%. 1-Aminohexamethyleneimine was identified by GC-MS and the fact that the holding time of GC of the standard sample coincided with the holding time of GC of the product. Example 17 Synthesis of pyrazolidine hydrochloric acid salt A 1-liter glass autoclave was charged with 226.1 g (3.30 moles) of hydrazine monohydrochloride, 111.4 g (1.10 moles) of concentrated hydrochloric acid, 83.7 g (1.10 moles) of 1,3-propanediol and 400.0 g of H 2 O, and with stirring, the above substances were reacted at 140 °C for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to recover white crystals. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), pyrazolidine hydrochloride in 393.1 g of the methanol mother liquor had a content of 20.16% (titrated), 79.25 g (0.73 mole), the formation rate 66.4%. Furthermore, the formation of tetrahydro-1H. 5H-pyrazolo-[1, 2-a]pyrazole as a by-product was confirmed. Pyrazolidine and tetrahydro-1H, 5H-pyrozolo-[1,2-a] pyrazole were identified by GC-MS. The reaction selectivity was 79.01% of pyrazolidine and 17.76% of tetrahydro-1H, SH-pyrazolo-[1. 2-a]pyrazole, and 3.23% of 1, 3-propanediol remained (GC). In the presence of an inorganic acid, 1,4-butanediol was reacted with hydrazine hydrohalogenic acid salt to give 1-aminopyrrolidine. Accordingly, if the same reaction proceeded in the case of 1,3-propanediol, trimethyleneimine would be presumably formed. But it could not be confirmed by a GC-MS analysis. The product was pyrazolidine in which two nitrogens of hydrazine are incorporated in a 5-membered ring. The cause of this case is ascribable to the magnitude of a distortion energy of trimethyleneimine (formula 16). Example 18 Synthesis of pyrazolidine hydrochloric acid salt A 1-liter glass autoclave was charged with 75.4 g (1.10 moles) of hydrazine monohydrochloride, 230.9 g (2.20 moles) of hydrazine dihydrochloride, 83.7 g (1.10 moles) of 1,3-propanediol and 400.0 g of H 2 O, and with stirring, the above substances were reacted at 140°C for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 233.8 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH to give hydrazine monohydrochloride 65.24% by weight, [152.53 g (2.23 moles), the recovery rate 101.23%] and HCl 31.67% by weight, [74.04 g (2.03 moles), the recovery rate 92.23%]. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), pyrazolidine hydrochloride in 109.6 g of the methanol mother liquor was 61.26% (titrated), 67.14 g (0.62 mole), and the formation rate was 56.2%. The reaction selectivity was 75.69% of pyrazolidine and 24.31% of tetrahydro-1H, 5H-pyrazolo-(1,2-a]pyrazole. Incidentally, 1,3-propanediol did not remain (GC). Example 19 Synthesis of pyrazolidine hydrochloride acid salt A 1-liter glass autoclave was charged with 150.7 g (2.20 moles) of hydrazine monohydrochloride, 115.5 g (1.10 moles) of hydrazine dihydrochloride, 83.7 g (1.10 moles) of 1, 3-propanediol and 400.0 g of H 2 O, and with stirring, the above substances were reacted at 140°C for 5 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 201.2 g of white crystals. The composition of the mixture was determined by titration with 1N-NaOH to give 80.89% by weight of hydrazine monohydrochloride [162.75 g (2.38 moles), the recovery rate 108.00%], and 17.55% by weight of HCl, [35.30 g (0.97 mole), the recovery rate 87.91%]. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), pyrazolidine hydrochloride in 109.7 g of the methanol mother liquor was 57.64% (titrated), 63.23 g (0.58 mole), and the formation rate was 52.9%. The reaction selectivity was 77.22% of pyrazolidine and 20.81% of tetrahydro-1H, 5H-pyrazolo-[1,2-a]pyrazole. It was found that 1.97% of 1,3-propanediol remained (GC). Example 20 Synthesis of 4-aminomorpholine hydrochloric acid salt A 1-liter glass autoclave was charged with 150.2 g (3.00 moles) of hydrazine hydrate, 405.1 g (4.00 moles) of concentrated hydrochloric acid, and 106.1 g (1.00 mole) of diethylene glycol, and with stirring, the above substances were reacted at 140°C for 10 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and a mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride) was washed with methanol to separate 144.4 g of white crystals. The composition of the mixture was titrated with 1N-NaOH to give hydrazine monohydrochloride 87.72% by weight, 119.45 g (1.74 moles), the recovery rate 87.18%, HCl 16.09% by weight, 23.23 g (0.64 mole), the recovery rate 63.65%. After separating the mixture of (hydrazine monohydrochloride + hydrazine dihydrochloride), a suitable amount of methanol was added to 133.2 g of the methanol mother liquor, and the hydrochloric acid content in the methanol mother liquor was neutralized with 35.5 g (0.89 mole) of sodium hydroxide. 4-Aminomorpholine in the methanol mother liquor was 4.47 g (0.044 mole), the formation rate 4.37%, diethylene glycol 67.7 g (0.638 mole), the conversion 36.2%. 4-Aminomorpholine and diethylene glycol were identified by GC-MS and the fact that the holding time of GC of the standard sample coincided with a holding time of GC of the product.

Claims: A process for producing an alicyclic hydrazine derivative and/or its hydrohalogenide, which comprises reacting a hydrazine hydrohalogenic acid and/or a salt thereof with a diol compound and/or an alicyclic ether compound in the presence of excess inorganic acid and/or a salt thereof. A process according to claim 1 wherein the hydrazine hydrohalogenic acid salt comprises a hydrazine hydromonohalogenic acid salt of formula (1) NH 2 NH 2 ·HX wherein X represents a halogen atom. A process according to claim 1 or claim 2 wherein the diol compound is of formula (2) HO-(CH 2 ) m -A-(CH 2 ) n -OH wherein A represents an oxygen atom, a methylene group or an ethylidene group, and each of m and n, which maybe the same or different, represents an integer of 1 to 3. A process according to claim 1, 2 or 3 wherein the alicyclic ether compound is of formula (3) wherein r represents an integer of 4 or 5. A process according to any preceding claim wherein the alicyclic hydrazine derivative is of formula (4) wherein A represents an oxygen atom, a methylene group or an ethylidene group, and each of m and n, which maybe the same or different, represents an integer of 1 to 3. A process according to any of claims 1 to 4 wherein the alicyclic hydrazine derivative is of formula (5) wherein p represents an integer of 3 to 4. A process according to claim 1 wherein the inorganic acid comprises a hydrohalogenic acid. A process according to claim 7 wherein the inorganic acid comprises hydrazine hydrodihalogenic acid. A process according to any preceding claim wherein the reaction is carried out at a mole ratio of the diol compound or alicyclic ether compound : hydrazine hydromonohalogenic acid and/or salt thereof : inorganic acid of 1 : 1-10 : 0.2-3, and at a temperature of 100 to 150°C, and at a pressure greater than atmospheric pressure. A process according to any preceding claim which additionally comprises: (a) concentrating a solution that results from the reaction and/or adding an alcohol solvent thereto, to cause precipitation of unreacted hydrazine hydrohalogenic acid and/or salt thereof; (b) removing precipitate from the solution; and (c) treating mother liquor resulting from that removal of precipitate to cause precipitation of alicyclic hydrazine derivative. A process according to any preceding claim wherein the diol compound comprises 1,4-butanediol and/or the alicyclic ether compound comprises tetrahydrofuran, and said alicyclic hydrazine derivative and/or its hydrohalogenic acid salt comprises 1-aminopyrriolidine and/or its hydrohalogenic acid salt, as the case may be.

Inventors: FUJITA HIROYUKI, HASEGAWA YOUICHI, HYODA SHUNJI, OKI YASUO, SAWADA HIROTOSHI, FUJITA, HIROYUKI, HASEGAWA, YOUICHI, HYODA, SHUNJI, OKI, YASUO, SAWADA, HIROTOSHI
Applicants: JAPAN HYDRAZINE CO LTD, JAPAN HYDRAZINE CO., LTD.
Application year: 1997
Main classification: C07D207
IPC codes: C07D487, C07D237, C07D295