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The preparation method of l-rhamnose dialkyl thioacetal compound

A technology of alkyl thioacetals and compounds, which is applied in the field of preparation of L-rhamnose dialkyl thioacetals, can solve the problems of not affecting the amount of glucosinolate by-products, environmental pollution, and high production costs

Inactive Publication Date: 2017-12-05
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] Since the glucosinolate by-products account for about 40%-50% of the crude product, and are similar in polarity to the corresponding thioacetal 7, it is difficult to remove the glucosinolate by-products by recrystallization. Therefore, using this method to obtain 5-deoxy- L - arabinose (4) yield is lower and lower quality
In addition, document CN104558065A reports that p-toluenesulfonic acid can be used instead of hydrochloric acid to catalyze L -Reaction of rhamnose with dodecanethiol to prepare thioacetal 7, but the method disclosed in the example of this document is only to obtain the crude product, and it is not stated whether the crude product contains glucosinolate by-products (9)
[0015] We found that by further repeating the above two documents (CN101090907A, CN104558065A), in L - rhamnose or L - When rhamnose monohydrate (1) reacts with dodecanethiol, no matter it is catalyzed by protonic acids such as concentrated hydrochloric acid, hydrogen chloride, p-toluenesulfonic acid, sulfuric acid or phosphoric acid, there will be 30%-60% glucosinolate side effects The product (9) is generated; and we also found that by changing the parameters of the reaction, such as: solvent type, reaction temperature, etc., the amount of glucosinolate by-products cannot be affected; although the purity of Thiamal 7, but the reaction yields are all lower than 50%
[0016] In summary, the 5-deoxy- L - Arabinose (4) synthesis technology, especially L - The preparation method of rhamnose dialkyl thioacetal compounds (I) has serious environmental pollution, expensive raw materials, many reaction by-products, low total yield and other deficiencies, which make 5-deoxy- L - The preparation cost of arabinose (4) is relatively high, and the large-scale preparation is limited

Method used

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  • The preparation method of l-rhamnose dialkyl thioacetal compound
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  • The preparation method of l-rhamnose dialkyl thioacetal compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] L - Preparation of rhamnose di(dodecyl) thioacetal (Ia)

[0027]

[0028] Add to the reaction bottle L - rhamnose monohydrate (55 mmol)), 1,4-dioxane (100 ml) and ZnCl 2 (10 mmol), after stirring evenly, add dodecylmercaptan (115 mmol), and stir at room temperature for 10 h. After the reaction, the reaction solution was added to deionized water (150 ml), filtered, and the filter cake was recrystallized with ethanol to obtain a white L - Rhamnose di(dodecyl) thioacetal solid, yield 92.0%, mp 112.4~113.9°C; 1 H NMR (CDCl 3) d: 4.90(s, 1H), 4.42(d, J =5.6 Hz, 1H), 4.17(s, 1H), 4.14~4.16(m, 1H), 4.07(d, J =7.6 Hz, 1H), 3.79~3.80(m, 2H), 3.54~3.59(m, 1H), 2.58~2.64(m, 4H), 1.51~1.55(t, J =6.8 Hz, 4H),1.25~1.34(m, 36H), 1.12(d, J =6.0 Hz, 3H), 0.86(t, J =5.6 Hz, 6H); HRMS (ESI) calcd for C 30 h 63 o 4 S 2 [M+H] + 551.4168, found 551.4160.

Embodiment 2

[0030] L - Preparation of rhamnose di(dodecyl) thioacetal (Ia)

[0031] The operation process is the same as in Example 1, except that 1,4-dioxane is replaced with 2-methyltetrahydrofuran, ZnCl 2 with TiCl 4 replace it with white L - Rhamnose di(dodecyl) thioacetal solid, yield 95.0%, mp 112~113°C.

Embodiment 3

[0033] L - Preparation of rhamnose di(dodecyl) thioacetal (Ia)

[0034] Operation process is the same as embodiment 1, just with 1,4-dioxane N,N - Dimethylformamide replacement, ZnCl 2 Replace with boron trifluoride ether to get white L - Rhamnose di(dodecyl) thioacetal solid, yield 93.0%, mp 112.2~113.6°C.

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Abstract

The invention discloses a method for preparing an L-rhamnose dialkyl mercaptal compound (I). According to the method, L-rhamnose or L-rhamnose monohydrate is adopted as a starting raw material and reacts with corresponding mercaptan without a solvent or in a proper solvent with Lewis acid as a catalyst, and the L-rhamnose dialkyl mercaptal compound (I) is obtained. The formula is shown in the specification, wherein R represents C6-18 alkyl, benzyl and 2-phenethyl.

Description

technical field [0001] The invention belongs to the field of medicinal chemistry and relates to a class of chemical structures as shown in (I) L - the preparation method of rhamnose dialkyl thioacetal compound, [0002] [0003] In the formula: R represents C 6-18 Alkyl, benzyl, 2-phenethyl. Background technique [0004] Sapropterin dihydrochloride, the chemical name is (6 R )-2-Amino-6-[(1 R ,2 S )-1,2-dihydroxypropyl]-5,6,7,8-tetrahydro-4(1 H )-pteridine dihydrochloride is a phenylalanine hydroxylase agonist developed by BioMarin Pharmaceuticals. It was first approved by the US FDA as an orphan drug in December 2007. The trade name is Kuvan, which is used to treat phenylacetone Uremia. This product is the first specific drug for the treatment of phenylketonuria, which has the characteristics of definite curative effect, convenient administration and high safety. [0005] At present, existing many literatures have reported the synthetic method of sapropterin dihy...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/14C07C323/12
CPCC07C319/14C07C323/12
Inventor 邓勇武梅强晓明李岩曹忠诚
Owner SICHUAN UNIV