TW391959B - Purification of sterically hindered 4-aminopiperidines - Google Patents

Description

87.12. Θ 2 彳 年 月 曰 曰 五 Supplementary V. Description of the invention (patent application No. 861074〇8 Chinese Version Correction Page (87 & The present invention is a method for purifying crude hexahydropyridine of formula I)

Its R1 to R4 are Cj-CV alkyl groups, or | ^ and chi 2 and / or CH2- chains of 2 to 5 carbons are formed from ^^ ~. The sterically hindered hexahydropyridine of formula I is widely used, especially as an intermediate in the preparation of UV stabilizers for synthetic polymers. Therefore, it is quite important that the hexahydropyridine I itself has as little coloring property as possible, and that this property can be retained for a long period of time even if a trace by-product is contained. Stereotropic 4-amine hexahydroeridine is produced industrially from acetone or acetone. The biological start 'Compound I can be in a single stage in the presence of ammonia and tritium. In a one-stage catalytic ring-closure reaction, from compounds!- -ο 装-(Please read the precautions on the back before filling in this page), 11

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (DE 2 4 1 2 75). Or in a single or two-stage hydrogenation reaction, prepared from triacetone amine, for example, under catalysis,

.11 '-4 This paper size applies to China National Standard (CMS) A4 specification (210X297 mm)

87.12. Θ 2 彳 年 月 曰 曰 五 Supplementary V. Description of the invention (patent application No. 861074〇8 Chinese Version Correction Page (87 & The present invention is a method for purifying crude hexahydropyridine of formula I)

Its R1 to R4 are Cj-CV alkyl groups, or | ^ and chi 2 and / or CH2- chains of 2 to 5 carbons are formed from ^^ ~. The sterically hindered hexahydropyridine of formula I is widely used, especially as an intermediate in the preparation of UV stabilizers for synthetic polymers. Therefore, it is quite important that the hexahydropyridine I itself has as little coloring property as possible, and that this property can be retained for a long period of time even if a trace by-product is contained. Stereotropic 4-amine hexahydroeridine is produced industrially from acetone or acetone. The biological start 'Compound I can be in a single stage in the presence of ammonia and tritium. In a one-stage catalytic ring-closure reaction, from compounds!- -ο 装-(Please read the precautions on the back before filling in this page), 11

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (DE 2 4 1 2 75). Or in a single or two-stage hydrogenation reaction, prepared from triacetone amine, for example, under catalysis,

.11 '-4 This paper size is applicable to Chinese National Standard (CMS) A4 specification (210X297 mm) Patent No. 86107408 ^ " —— One-to-One Chinese Manual Correction Page (^ year to month) ·, taxi \ 7 Year and month θ M t 1 M w, '% 七 7. ^ Π,. 2, .....-........ J. 1 Supplement (see in For example, DE2040975, DE2349962, DE2621870, EP33529, EP42119, EP303279, EP410970, EP611137, EP623585 and DE42 (0311). These industrially prepared sterically hindered amine hexahydropyridines are generally purified by distillation. However, the hexahydropyridine j prepared by the conventional technique usually still contains a disturbing coloring substance, or these substances may be formed after a short time. In order to overcome such conditions, it is known that, for example, in EP477 593, the color problem of the crude product N-alkyldialkanolamine can be improved by adding metal boron gaseous distillation and performing distillation under specific conditions and in the presence of water. However, the N-alkyl dialkanolamine is completely different from the sterically hindered 4-amine hexahydropyridine of the present invention in the class I substance. It is further known from Spec Chem 4 (M), US, US 3,159,276, 1153,207,790, and 1 ^ 3,222,3 1 0. After d or after distillation, sodium borohydride is added to ethanolamine, ethyleneamine or arylamine. It is feasible to improve the product color. However, this document does not mention hexahydropyridine, let alone specific distillation techniques. In contrast, the formation of high-purity steric heart amine hexahydropyridine takes a very different route. It is known in the printing of kDD2 6 6 799 by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs that hexahydropyridine 丨 is reacted with dioxidation in an acetone / water solution, after which the precipitate is separated and washed with acetone, followed by thermal decomposition The product was purified by distillation. su 丨 8 ii 527 describes another purification technique of steric hindrance I 4_amine hexahydropyridine 丨 · The contaminated crude product is dissolved in an aprotic solvent and reacted with ethylene glycol, the reaction product is distilled and subjected to several Steps for purification. Both of these technologies are extremely laborious and costly. Therefore, the purpose of the present invention is to provide a cost-effective method. -5-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Patent No. 86107408 ^ " —— One-to-one Chinese specification amendment Page (^ year by month) ..., taxi \ 7 year month θ M t 1 M w, '% 七 7. ^ Π,. 2, .....-........... ....... J. 1 supplements (see for example DE2040975, DE2349962, DE2621870, EP33529, EP42119, EP303279, EP410970, EP611137, EP623585 and DE42) 0311). These industrially prepared sterically hindered amine hexahydropyridines are generally purified by distillation. However, the hexahydropyridine j prepared by the conventional technique usually still contains a disturbing coloring substance, or these substances may be formed after a short time. In order to overcome such conditions, it is known that, for example, in EP477 593, the color problem of the crude product N-alkyldialkanolamine can be improved by adding metal boron gaseous distillation and performing distillation under specific conditions and in the presence of water. However, the N-alkyl dialkanolamine is completely different from the sterically hindered 4-amine hexahydropyridine of the present invention in the class I substance. It is further known from Spec Chem 4 (M), US, US 3,159,276, 1153,207,790, and 1 ^ 3,222,3 1 0. After d or after distillation, sodium borohydride is added to ethanolamine, ethyleneamine or arylamine. It is feasible to improve the product color. However, this document does not mention hexahydropyridine, let alone specific distillation techniques. In contrast, the formation of high-purity steric heart amine hexahydropyridine takes a very different route. It is known in the printing of kDD2 6 6 799 by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs that hexahydropyridine 丨 is reacted with dioxidation in an acetone / water solution, after which the precipitate is separated and washed with acetone, followed by thermal decomposition The product was purified by distillation. su 丨 8 ii 527 describes another purification technique of steric hindrance I 4_amine hexahydropyridine 丨 · The contaminated crude product is dissolved in an aprotic solvent and reacted with ethylene glycol, the reaction product is distilled and subjected to several Steps for purification. Both of these technologies are extremely laborious and costly. Therefore, the object of the present invention is to provide a cost-effective method. -5-This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) No. 86107048: Stripped: Unclaimed, Chinese Manual revision page (December 87) 11-1111- 11.1, — 1

V. Description of the invention (The method of the present invention can be used to prepare a high-purity, color-stable steric obstacle 4: amine hexahydrogen. That is, the product can maintain low-level colorability and low content of by-products such as stable auxiliary agents for a long time. ° We have found that this is achieved by the method described above, which includes, in the first step, the high boiling point substance and, if present, water, are removed from the crude hexahydropyrene through distillation; in the second step, The reducing agent is added in an amount of 0.01-5% of the weight of the product in the first step; and in the third step, the hexahydro P ratio is separated by distillation. Other features of the present invention are detailed in the appendix to the scope of the patent application. Carcass barrier 4 In the amine hexahydropyridine, the above ^ and ^ are preferably (^-(: 3 alkyl, especially ethyl or methyl, such as methyl. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs.) The original agent is generally a solid material in the standard state. The preferred compound is MXH4_mYra, where M is an alkali metal, and NR4, in which each size is the same or different Ci-C: 4 alkyl, or i-equivalent alkaline earth metal. Or 1 equivalent of zinc is preferred In particular, it is oriented or unloaded, for example, when it is sodium, X is Ming or especially, Y.CN or preferably hydrogen, and melamine is} or 〇 or especially 〇. Example I-is sodium borohydride, It has been found that (RaO) 2TiBH4 or (Ra〇) 3TiBH4, where Ra is C! -C4-alkyl, is suitable for use in the present invention. The novel method can be used in the atmosphere or preferably under reduced pressure, especially 1 〇_2〇〇mbar ', for example, from 20-100 mbar, continuous or batch. F1 * Unless otherwise specified, otherwise the boiling point or boiling point range defined in the present invention is related to a pressure of 40 mbar The tester is about the purification of 4-amine_2,2,6,6, -hexahydropyridine in each case. For other amines hexahydropyridine, the skilled person can derive appropriate conditions through simple experiments. —6 -This paper is suitable for home finances (CNS) ~ inspection (Xin Xin Mi No. 86107074): Unclaimed, Chinese manual amendment page (December 87) 11-1111- 11.1, — One

V. Description of the invention (The method of the present invention can be used to prepare a high-purity, color-stable steric obstacle 4: amine hexahydrogen. That is, the product can maintain low-level colorability and low content of by-products such as stable auxiliary agents for a long time. ° We have found that this is achieved by the method described above, which includes, in the first step, the high boiling point substance and, if present, water, are removed from the crude hexahydropyrene through distillation; in the second step, The reducing agent is added in an amount of 0.01-5% of the weight of the product in the first step; and in the third step, the hexahydro P ratio is separated by distillation. Other features of the present invention are detailed in the appendix to the scope of the patent application. Carcass barrier 4 In the amine hexahydropyridine, the above ^ and ^ are preferably (^-(: 3 alkyl, especially ethyl or methyl, such as methyl. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs.) The original agent is generally a solid material in the standard state. The preferred compound is MXH4_mYra, where M is an alkali metal, and NR4, in which each size is the same or different Ci-C: 4 alkyl, or i-equivalent alkaline earth metal. Or 1 equivalent of zinc is preferred In particular, it is oriented or unloaded, for example, when it is sodium, X is Ming or especially, Y.CN or preferably hydrogen, and melamine is} or 〇 or especially 〇. Example I-is sodium borohydride, It has been found that (RaO) 2TiBH4 or (Ra〇) 3TiBH4, where Ra is C! -C4-alkyl, is suitable for use in the present invention. The novel method can be used in the atmosphere or preferably under reduced pressure, especially 1 〇_2〇〇mbar ', for example, from 20-100 mbar, continuous or batch. F1 * Unless otherwise specified, otherwise the boiling point or boiling point range defined in the present invention is related to a pressure of 40 mbar The tester is about the purification of 4-amine_2,2,6,6, -hexahydropyridine in each case. For other amines hexahydropyridine, the skilled person can derive appropriate conditions through simple experiments. —6 -This paper is suitable for home finance (CNS) ~ Experience (Jin Xin Mi No. 80107074)

V. Description of the invention (Generally referred to as “boiling point substances” printed by employees' consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, those who have a boiling point of at least 35 above the desired product at a pressure of 40 mbar. _Amine_ In 2,2,6,6-tetramethylhexahydropyridine, high-boiling substances are removed by distillation, for example, at 140 ° C and 40 mbar. In the first step, the crude product High boiling point substances are completely removed by distillation, and, in a particular embodiment of the present invention, water is removed. Generally, (a) rectification is performed in which high boiling point substances are removed in the liquid phase and water It is removed from the top of the rectification column in a single step, or the crude product is distilled off from the high-boiling point substance by distillation in a suitable device, such as a leaf wiper 'falling film still or stirred vessel connected to a concentrator', Distillation is then performed to remove the water. The separation of the water is not important and can be carried out at, for example, 100 mbar, 40-50 ° C or under suitable different pressures. To separate high-boiling substances, distill The liquid phase is usually heated to 140 ° C (under 40 mbar). Better As a result, hexahydropyridine I with a small amount of high-boiling substances is obtained. In general, hexahydropyridine hydrazone containing less than 0.1% by weight of high-boiling components is still acceptable, however, the content of high-boiling components is preferred It is less than 0.01% by weight of hexaargyridine. The water content is not important and is usually adjusted to 1 ° / of the weight of hexahydropyridine. _ Following 0 Next, in the second step, a reducing agent is added, and the weight is generally added as 〇. 〇1-2% of the amount can be obtained with the desired properties of colorless products' preferably to use 0. 0 1 -1% by weight, especially 0. 〇0 0. 5%. Add the method and It is not important; the reducing agent can usually be added to the liquid phase of the 馆 'kan in the form of powder or solution. After adding the reducing agent, the product is purified by steaming.' Usually the Chinese paper standard (CNS) A4 is applicable to this paper standard. Specifications (21〇χ297mm) Please read the precautions for back ft first

Fee 褽 .1% Special Collection No. 80107074

V. Description of the invention (Generally referred to as “boiling point substances” printed by employees' consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, those who have a boiling point of at least 35 above the desired product at a pressure of 40 mbar. _Amine_ In 2,2,6,6-tetramethylhexahydropyridine, high-boiling substances are removed by distillation, for example, at 140 ° C and 40 mbar. In the first step, the crude product High boiling point substances are completely removed by distillation, and, in a particular embodiment of the present invention, water is removed. Generally, (a) rectification is performed in which high boiling point substances are removed in the liquid phase and water It is removed from the top of the rectification column in a single step, or the crude product is distilled off from the high-boiling point substance by distillation in a suitable device, such as a leaf wiper 'falling film still or stirred vessel connected to a concentrator', Distillation is then performed to remove the water. The separation of the water is not important and can be carried out at, for example, 100 mbar, 40-50 ° C or under suitable different pressures. To separate high-boiling substances, distill The liquid phase is usually heated to 140 ° C (under 40 mbar). Better As a result, hexahydropyridine I with a small amount of high-boiling substances is obtained. In general, hexahydropyridine hydrazone containing less than 0.1% by weight of high-boiling components is still acceptable, however, the content of high-boiling components is preferred It is less than 0.01% by weight of hexaargyridine. The water content is not important and is usually adjusted to 1 ° / of the weight of hexahydropyridine. _ Following 0 Next, in the second step, a reducing agent is added, and the weight is generally added as 〇. 〇1-2% of the amount can be obtained with the desired properties of colorless products' preferably to use 0. 0 1 -1% by weight, especially 0. 〇0 0. 5%. Add the method and It is not important; the reducing agent can usually be added to the liquid phase of the 馆 'kan in the form of powder or solution. After adding the reducing agent, the product is purified by steaming.' Usually the Chinese paper standard (CNS) A4 is applicable to this paper standard. Specifications (21〇χ297mm) Please read the precautions for back ft first

Fee 褽 .1% Fine 59 Patent No. 86107408 Revised Chinese Manual

V. Description of the invention 4.9% medium and high boiling point materials are distilled at MO ° C and 40 mbar using a wiper evaporator (200 cm2 evaporator surface area, 400 rpm). The feed rate was 500 g / h (preheated to 100 ° C), the liquid phase temperature was 106 ° C, and the top temperature was 89. (:, 2560 grams (92.3%) are distilled off. The components after distillation are as follows: 8 7.2% triacetone diamine 9.9% water 1.5% low-boiling substances 1.4% medium and high-boiling substances Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The printed crude TAD product is separated from high-boiling substances through a 2.4-meter Sulzer_CY-filled column (approximately η theoretical plate 'width of 43 mm) at a pressure of 100 mbar and reflux at a ratio of 5: 1 When the temperature at the top of the column is 43-44 ° C, 256 g of water is distilled off first. During the distillation, 〇 丨 sodium borohydride in the liquid phase is added and the continuous distillation is performed at 40 mbar. The temperature at the top of the column At 8 o'clock, the separated distillate contained 8 5-9% TAD (11 1 g), and further fractionated at the top temperature of 99.0 o'clock. The separated distillate contained 9S 4% TAD (24.0 g). ). At the top temperature of 99-102 ° C, the main distillate of the rectification contained a purity of 99 8 0 / (GC) 1 786 g T AD, and the yield of the steamhouse was 77%. A) Pure The TAD color was stable for at least 5 weeks (APhA color number 値 <50). The results are shown in the table below. B) The TAD sample obtained by this technology is stored under the addition of 110 ppm sodium borohydride. After this addition, the TAD product is indeed colorless for at least 5 weeks. In addition, its color is stable. 5. Samples (A) and (B) were stored at room temperature and sunk. This paper scale is applicable to China ^ 1 ^ 7 ^ -2; &gt; &lt; 297. V. Description of the invention (5's completed crane tower, such as a slab tower or a packed tower, preferably the latter with a different reflux ratio operation, The artiste ⑨ ^ ..ai, ^, has applied the pre-experiment and the 4 speed h has been proven to be suitable for removing the product flow ratio ^ to 10: 1, especially from 3 : 1 to 7: 1. The product 4_amine_2,2,6,6_tetratylhexahydropyridine is at 101 ... and boils at 40 mbar, as can be easily detected by the skilled person (for example, J TP〇lvm ς ^, Ώ ^ ^ .. • rlym. BC1 ·, Part A-1, 10⑴), (1972) 3295-310). Therefore, it is generally available at 96-103 (under 40 mbar). For products that are colorless in nature, a small amount of reducing agent can be added to increase the stability during storage. The reducing agent is usually the above-mentioned substance, and it is generally added to 0_001_0.02 // by weight of the product. In general, a reducing dose of up to 200 ppm is sufficient. In special cases, 〇〇〇_, 50 or 10 ppm is sufficient. This novel method provides a simple and cost-effective way to provide pure sterically hindered 4-amine hexahydropyridine I, which is indeed colorless and can be used during storage 'with very low levels of by-products such as stabilizers. At the same time keep the color stable. Example Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economics. The color determination of 4-aminehexahydropyridine I for steric disorders is determined by DIN-JSO 627 1 for the APHA color number. Example 1 Crude 4-amine-2.; 2,6,6-tetrahydropyridine contains the following ingredients: 83.6% triacetone diamine (TAD) 10.0% water 1.5% low boiling point substance This paper applies to China National Standard (CNS) Α4 Specification (210X297 mm) J91959 No. 861〇74〇8 Patent History, please revise page of Chinese specification ------- 丨 ---- V. Description of invention (Please read the precautions in the back first (43 耄 m), reflux distillation at a pressure of 100 mbar at a ratio of 5: 1. 43-44 at 100 mbar. (: 349 grams of the original German extract mainly containing water was distilled off at that time. Next, 3.0 grams (by weight 〇 · 丨 〇 /.) Of sodium borohydride was added in a distillation liquid phase containing less than 0.1% water. After the TAD of 222 g of the initial distillate has a purity of 99.0%, the main distillate can be obtained at a pressure of 40 mbar at the top temperature of the column 9: TC, which contains 2 丨 丨g of TAD with a purity of 99.7% and a water content of &lt; 〇%, a distillation yield of 2 丨 6 g (82%). Stored in nitrogen in the dark for two days, the resulting pure TAD product turned yellow (APHA Color number 値> 100). Comparative Example 2 Order 4208 g of crude TAD composition 85.6% triacetone diamine (TAD) 9.0% water 0.7% low boiling point substance 4.7% medium and high boiling point substance consumption by the Central Standards Bureau of the Ministry of Economic Affairs Cooperatives are printed at a pressure of 100 to 40 mbar through a 2.4-meter Sulzer-CY-filled column (approximately 22 theoretical laminates, with a width of 43 mm) and returned to the fine hall at a ratio of 5: 1. Then under the grinding force of 100 bar and at 43-44 o'clock, water was separated from the output of the starting hall, under the pressure of 40 mbar, the temperature of the top of the tower was 97-1 03 ° C. At that time, the main library output was obtained, which contained a pure TAD distillate with a TAD content &gt; 99.6% (GC). The steam-saturated yield: 3022 g (84%). Pure distillate (GC measured T AD content 99 · 7%) stored in borohydride-free steel, and stored in sodium borohydride, as in Example 1, and measured, the results are shown as -11-This paper size applies Chinese National Standard (CNS) Α4 specification (2 丨0X297 mm) Fine 59 Chinese Patent No. 86107408 Revised Page

V. Description of the invention 4.9% medium and high boiling point materials are distilled at MO ° C and 40 mbar using a wiper evaporator (200 cm2 evaporator surface area, 400 rpm). The feed rate was 500 g / h (preheated to 100 ° C), the liquid phase temperature was 106 ° C, and the top temperature was 89. (:, 2560 grams (92.3%) are distilled off. The components after distillation are as follows: 8 7.2% triacetone diamine 9.9% water 1.5% low-boiling substances 1.4% medium and high-boiling substances Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The printed crude TAD product is separated from high-boiling substances through a 2.4-meter Sulzer_CY-filled column (approximately η theoretical plate 'width of 43 mm) at a pressure of 100 mbar and reflux at a ratio of 5: 1. When the temperature at the top of the column is 43-44 ° C, 256 g of water is distilled off first. During the distillation, 〇 丨 sodium borohydride in the liquid phase is added and the continuous distillation is performed at 40 mbar. The temperature at the top of the column At 8 o'clock, the separated distillate contained 8 5-9% TAD (11 1 g), and further fractionated at the top temperature of 99.0 o'clock. The separated distillate contained 9S 4% TAD (24.0 g). ). At the top temperature of 99-102 ° C, the main distillate of the rectification contained a purity of 99 8 0 / (GC) 1 786 g T AD, and the yield of the steamhouse was 77%. A) Pure The TAD color was stable for at least 5 weeks (APhA color number 値 <50). The results are shown in the table below. B) The TAD sample obtained by this technology is stored under the addition of 110 ppm sodium borohydride. After this addition, the TAD product is indeed colorless for at least 5 weeks. In addition, its color is stable. 5. Samples (A) and (B) were stored at room temperature and sunk. This paper size is applicable to China ^ 1 ^ 7 ^ -2; &gt; &lt; 297 public 391959 V. Description of the invention (7) Number of days of storage 値 Color (undiluted product) (A) Without NaBH4 (B) Added 1 1 Oppm NaBH4 13 43 5 14 37 6 16 37 5 18 38 4 19 40 3 20 38 .7 21 41 11 22 36 8 25 48 13 32 36 3 39 43 4 Comparative example 1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2987 grams of crude TAD contains 8 7.2% triacetone diamine: 8.7% water, about Μ%, low boiling point materials, 4.0% medium and high boiling point materials. Use a 2.4 m Sulzer-CY packed column (about 22 theoretical laminates, width

TA 1 / J i τ * y ZX υ ζ J91959 Patent History No. 861〇74〇8 please revise the Chinese instruction manual ------- 丨 ---- V. Description of the invention (Please read the precautions of the back first , 43 耄 m), reflux distillation at a pressure of 100 mbar at a ratio of 5: 1. 43-44 at 100 mbar. (: 349 grams of the original German extract mainly containing water was distilled off at that time. Next, 3.0 grams (by weight 〇 · 丨 〇 /.) Of sodium borohydride was added in a distillation liquid phase containing less than 0.1% water. After the TAD of 222 g of the initial distillate has a purity of 99.0%, the main distillate can be obtained at a pressure of 40 mbar at the top temperature of the column 9: TC, which contains 2 丨 丨g of TAD with a purity of 99.7% and a water content of &lt; 〇%, a distillation yield of 2 丨 6 g (82%). Stored in nitrogen in the dark for two days, the resulting pure TAD product turned yellow (APHA Color number 値> 100). Comparative Example 2 Order 4208 g of crude TAD composition 85.6% triacetone diamine (TAD) 9.0% water 0.7% low boiling point substance 4.7% medium and high boiling point substance consumption by the Central Standards Bureau of the Ministry of Economic Affairs Cooperatives are printed at a pressure of 100 to 40 mbar through a 2.4-meter Sulzer-CY-filled column (approximately 22 theoretical laminates, with a width of 43 mm) and returned to the fine hall at a ratio of 5: 1. Then under the grinding force of 100 bar and at 43-44 o'clock, water was separated from the output of the starting hall, under the pressure of 40 mbar, the temperature of the top of the tower was 97-1 03 ° C. At that time, the main library output was obtained, which contained a pure TAD distillate with a TAD content &gt; 99.6% (GC). The steam-saturated yield: 3022 g (84%). Pure distillate (GC measured T AD content 99 · 7%) stored in borohydride-free steel, and stored in sodium borohydride, as in Example 1, and measured, the results are shown as -11-This paper size applies Chinese National Standard (CNS) Α4 specification (2 丨0X297 mm)

Sil.859 A7 ----- B7 V. Description of the invention (9) 'The following table ♦ · |-Color number 未 (undiluted product): (according to DIN-ISO 6271) Storage days without adding NaBH4 • —— * 1000 ppm 1OOppm 1 238 207 225 3 297 16 61 4 ~ 1 289 12 35 5 2 87 -----— -—. -— 10 27 6 286 9 32 10 ----- 299 5 73 11 297 4 172 42 309 3 255 please. After reading the note of ίτ, note that f 再 Even if a large amount of reducing agent (0.1./. = 丨 0 0 0 ppm) is added to improve the color shift degree, it will increase the ratio of undesired by-products. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs on paper

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Claims (1)

0 ^ 1 ^ 59 Patent Application No. 86107408 Chinese Patent Application Range Amendment (December of the following year) A8 B8 C8 D8 Patent Application Range L this 1: Purified formula I crude hexahydrogen P ratio The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs prints its R to R—Ci-C ^ -base, or riri to form a 2 to 5 carbon CH2 chain—which includes, the first step, by steaming The museum will remove one high and one lag-point ~ substance one-and 'if present, water is removed from the crude hexahydropyridine; in the second step, it is added as 0.0 1-5% of the weight of the product in the first step. 1; and, the third step, the separation of hexahydroeridine by distillation; wherein the rhenium agent is a compound of the formula MXH4-mYm, the toe of which is a blue metal, NR *, each of which may be the same or different alkyl group, or j Equivalent t alkaline earth-metal or 1 equivalent of zinc, χ is boron or aluminum, γ is hydrogen or CM, and m is 0 or 1. 2. The method according to item 4. of the patent application, in which rI, R2, Han 3 and Chi 4 are α-α3 · alkyl-. 3. According to—Application. The method of item i of the patent scope, in which hexahydro 1? Specific bite weight I &lt; 0.0 (H-0.0 2% of reducing agent) is added. In pyridine I. [From R2 and / or R3 and R4— (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 0 ^ 1 ^ 59 No. 86107408 Patent Application Chinese Patent Application Range Amendment (December of the following year) A8 B8 C8 D8 Patent Application Range L Version 1: Purified Formula I crude hexahydrogen P ratio The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs prints its R to R—Ci-C ^ -base, or riri to form a 2 to 5 carbon CH2 chain—which includes, the first step, by steaming The museum will remove one high and one lag-point ~ substance one-and 'if present, water is removed from the crude hexahydropyridine; in the second step, it is added as 0.0 1-5% of the weight of the product in the first step. 1; and, the third step, the separation of hexahydroeridine by distillation; wherein the rhenium agent is a compound of the formula MXH4-mYm, the toe of which is a blue metal, NR *, each of which may be the same or different alkyl group, or j Equivalent t alkaline earth-metal or 1 equivalent of zinc, χ is boron or aluminum, γ is hydrogen or CM, and m is 0 or 1. 2. The method according to item 4. of the patent application, in which rI, R2, Han 3 and Chi 4 are α-α3 · alkyl-. 3. According to—Application. The method of item i of the patent scope, in which hexahydro 1? Specific bite weight I &lt; 0.0 (H-0.0 2% of reducing agent) is added. In pyridine I. [From R2 and / or R3 and R4— (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)