WO2001002336A1 - Process for the production of glycerol dinitrates - Google Patents

Process for the production of glycerol dinitrates Download PDF

Info

Publication number
WO2001002336A1
WO2001002336A1 PCT/GB2000/002515 GB0002515W WO0102336A1 WO 2001002336 A1 WO2001002336 A1 WO 2001002336A1 GB 0002515 W GB0002515 W GB 0002515W WO 0102336 A1 WO0102336 A1 WO 0102336A1
Authority
WO
WIPO (PCT)
Prior art keywords
dinitrate
glycidol
glycerol
product
reacting
Prior art date
Application number
PCT/GB2000/002515
Other languages
French (fr)
Inventor
Martin Eamon Colclough
Javid Hamid
Gurvinder Singh Kang
Andrew Pelter
Original Assignee
Qinetiq Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qinetiq Limited filed Critical Qinetiq Limited
Priority to AU55576/00A priority Critical patent/AU5557600A/en
Publication of WO2001002336A1 publication Critical patent/WO2001002336A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/02—Preparation of esters of nitric acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to methods for the production, independently, of glycerol-1,2- and 1,3-dinitrates (1,2- or l,3-dinitrato-2-hydroxypropane or 1,2- or 1,3- dinitroglycerine).
  • Hakimelahi et al have described the use of either thionyl chloride nitrate or thionyl nitrate as the nitrating agent in the preparation specifically of the 1,3-dinitrate in 70% yield.
  • the use of silver nitrate to produce the nitrating agent makes the process relatively expensive and the non-quantitative yield means that extensive separation efforts are required in order to arrive at the desired product in pure form.
  • the present invention provides a process for the preparation of glycerol 1,2- or glycerol 1,3-dinitrate from glycidol which comprises the steps of:
  • step (b) reacting the glycidol derivative from step (a) with dinitrogen pentoxide under anhydrous conditions in order to form the corresponding dinitrato compound;
  • step (b) removing the protective group from the product of step (b) to obtain the glycerol 1,2-dinitrate or glycerol 1,3-dinitrate product as the case may be.
  • step (a) is conveniently accomplished using acetyl chloride or acetyl bromide in the presence of triethylamine at a temperature of below 5°C, preferably around 0°C, in dichloromethane.
  • the product is purified by aqueous workup followed by distillation.
  • Other methods for accomplishing step (a) would include use of acetic anhydride in the presence of a catalyst such as trimethylsilyl trifluoromethanesulphonate.
  • Step (c) of this process is conveniently carried out by the use of potassium carbonate in methanol.
  • other deprotection procedures such as treatment with iodine/methanol, p-toluenesulphonic acid/methanol and hydrochloric acid/methanol could be used.
  • the protected derivative of glycidol is added to an eqimolar amount of N 2 O 5 in dry dichloromethane at sub-ambient temperature (preferably below 10°C, most preferably at about -5 to 5°C) and left to stir at this temperature for about 2 hours before being allowed to warm up to ambient temperature and left for a further hour.
  • sub-ambient temperature preferably below 10°C, most preferably at about -5 to 5°C
  • step (a) is conveniently carried out by reaction of the glycidol with t-butyldimethylsilyl chloride in dry dichloromethane followed by slow addition to the reaction mixture of triethylamine. A temperature of below 5°C is again suitable for this step, as with the preparation of the 1,3 isomer. After stirring for 8 to 10 hours, pentane is added to the mixture and the mixture filtered to provide, after concentration, a residue from which the product may be distilled.
  • other analagous reagents with at least one higher alkyl substituent may be used.
  • the corresponding trimethylsilyl compound is not suitable as it is subject to reaction with the N 2 O 5 nitrating agent and likewise silyl species which contain aromatic substituents such as benzyl or phenyl groups are unsuitable for use because of the competing reaction of N 2 O 5 to nitrate the aromatic ring of the substituent.
  • trialkylsilyl ether derivative is used herein in relation to the process of the present invention to mean a trialkylsilyl ether derivative in which at least one of the alkyl groups is a propyl group or preferably a butyl or higher alkyl group.
  • step (c) involves the use of well- known reagents for removing the silyl ether protecting group such as 2,3-dichloro-5,6- dicyano-l,4-benzoquinone (DDQ), lithium chloride in dimethylformamide, eerie ammonium nitrate, iodine or tetrabutylammonium fluoride/boron trifluoride complex for example.
  • DDQ 2,3-dichloro-5,6- dicyano-l,4-benzoquinone
  • DDQ 2,3-dichloro-5,6- dicyano-l,4-benzoquinone
  • lithium chloride in dimethylformamide eerie ammonium nitrate, iodine or tetrabutylammonium fluoride/boron trifluoride complex for example.
  • Other variations of the reaction conditions detailed above for the protection and deprotection steps shall be encompassed within the scope of the invention.
  • a three-necked round-bottom flask (100 cm 3 ) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel.
  • the flask was charged with glycidol (0.74 g, 10 mmol) in dry dichloromethane (DCM)(30 cm 3 ) followed by the addition of t-butyldimethylsilyl chloride (1.65 g, 11 mmol) in dichloromethane (30 cm 3 ) at 0°C via the pressure equalised dropping funnel.
  • the reaction was allowed to stir for 30 minutes before slow addition of triethylamine (1.11 g, 11 mmol in 10 cm 3 of DCM).
  • a three-necked round-bottom flask (100 cm 3 ) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel.
  • the flask was charged with glycidol t-butyldimethylsilyl ether (0.36 g, 2 mmol) in dry dichloromethane (20 cm 3 ) followed by N2O5 (0.33 g, 3 mmol) in dichloromethane (20 cm 3 ) at 0°C.
  • the reaction was allowed to stir for 2 h at 0°C and then at ambient for a further 1 h.
  • a three-necked round-bottom flask (100 cm 3 ) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidol (1.16 g, 10 mmol) in dry dichloromethane (30 cm 3 ) followed by acetyl
  • a three-necked round-bottom flask (100 cm 3 ) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidyl acetate (0.23 g, 2 mmol) in dry dichloromethane (20 cm 3 ) followed by N 2 O 5 (0.33 g, 3 mmol) in dichloromethane (20 cm 3 ) at 0°C. The reaction was allowed to stir for 2 h at 0°C and then at ambient for a further 1 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for preparing either the 1,2-dinitrate or the 1,3-dinitrate of glycerol involves protecting glycidol respectively with either trialkylsilyl ether group or an acetate group then nitrating with dinitrogen pentoxide under anhydrous conditions, after which the protecting group is removed. High yields of exclusively the desired isomer are obtained avoiding the difficulties of isomer separation which arise with conventional methods.

Description

PROCESS FOR THE PRODUCTION OF GLYCEROL DINITRATES
The present invention relates to methods for the production, independently, of glycerol-1,2- and 1,3-dinitrates (1,2- or l,3-dinitrato-2-hydroxypropane or 1,2- or 1,3- dinitroglycerine).
Both the 1,2- and 1,3-dinitrates of glycerol have potential application in the synthesis of new energetic materials and as pharmaceuticals, for the alleviation of heart complaints.
Synthesis of dinitroglycerine (either 1,2- or l,3-dinitrato-2-hydroxypropane) has heretofore been achieved generally by mixed acid nitration of glycerol but this inevitably leads to a mixture of the isomers which are extremely difficult to then separate. Moreover the yield of the dinitrated product by this route is not very good as the reaction mixture further includes both mono- and tri-nitrated species, and these also have to be separated off in order to obtain the desired nitro-compounds.
Hakimelahi et al (Helv. Chim. Acta 67, 906 (1984)) have described the use of either thionyl chloride nitrate or thionyl nitrate as the nitrating agent in the preparation specifically of the 1,3-dinitrate in 70% yield. The use of silver nitrate to produce the nitrating agent makes the process relatively expensive and the non-quantitative yield means that extensive separation efforts are required in order to arrive at the desired product in pure form.
The applicant has now found that by use of the unconventional nitrating agent dinitrogen pentoxide in conjunction with other relatively straightforward process steps it is not only possible to achieve synthesis of specifically either the 1,2- or the 1,3- dinitrate under mild conditions but also in high (virtually quantitative) yield. In the case of the 1,3-dinitrate preparation route this result is particularly surprising as on the basis of all previous knowledge the expected product would be the 1,2-dinitrate. However, by the present method none of the latter isomer is produced. Instead that material may be obtained in high yield by use of a variation on the preparative method for the 1,3-dinitrate.
Accordingly the present invention provides a process for the preparation of glycerol 1,2- or glycerol 1,3-dinitrate from glycidol which comprises the steps of:
a) preparing either the acetate derivative of glycidol where the desired product is the 1,3-dinitrate or a trialkylsilyl ether derivative (as hereinafter defined) where the desired product is the 1,2-dinitrate;
b) reacting the glycidol derivative from step (a) with dinitrogen pentoxide under anhydrous conditions in order to form the corresponding dinitrato compound; and
c) removing the protective group from the product of step (b) to obtain the glycerol 1,2-dinitrate or glycerol 1,3-dinitrate product as the case may be.
For the preparation of the 1,3-dinitrate, step (a) is conveniently accomplished using acetyl chloride or acetyl bromide in the presence of triethylamine at a temperature of below 5°C, preferably around 0°C, in dichloromethane. The product is purified by aqueous workup followed by distillation. Other methods for accomplishing step (a) would include use of acetic anhydride in the presence of a catalyst such as trimethylsilyl trifluoromethanesulphonate.
Step (c) of this process is conveniently carried out by the use of potassium carbonate in methanol. Alternatively, other deprotection procedures such as treatment with iodine/methanol, p-toluenesulphonic acid/methanol and hydrochloric acid/methanol could be used.
In the nitration step (b) for either process, the protected derivative of glycidol is added to an eqimolar amount of N2O5 in dry dichloromethane at sub-ambient temperature (preferably below 10°C, most preferably at about -5 to 5°C) and left to stir at this temperature for about 2 hours before being allowed to warm up to ambient temperature and left for a further hour. A simple aqueous workup followed by removal of the organic solvent gives the pure glycerol dinitrate product.
For the preparation of the 1,2-dinitrate, step (a) is conveniently carried out by reaction of the glycidol with t-butyldimethylsilyl chloride in dry dichloromethane followed by slow addition to the reaction mixture of triethylamine. A temperature of below 5°C is again suitable for this step, as with the preparation of the 1,3 isomer. After stirring for 8 to 10 hours, pentane is added to the mixture and the mixture filtered to provide, after concentration, a residue from which the product may be distilled. As an alternative to the use of the t-butyldimethylsilyl chloride, other analagous reagents with at least one higher alkyl substituent may be used. The corresponding trimethylsilyl compound is not suitable as it is subject to reaction with the N2O5 nitrating agent and likewise silyl species which contain aromatic substituents such as benzyl or phenyl groups are unsuitable for use because of the competing reaction of N2O5 to nitrate the aromatic ring of the substituent.
Accordingly the term "trialkylsilyl ether derivative" is used herein in relation to the process of the present invention to mean a trialkylsilyl ether derivative in which at least one of the alkyl groups is a propyl group or preferably a butyl or higher alkyl group.
In the case of the 1,2-dinitrate preparation, step (c) involves the use of well- known reagents for removing the silyl ether protecting group such as 2,3-dichloro-5,6- dicyano-l,4-benzoquinone (DDQ), lithium chloride in dimethylformamide, eerie ammonium nitrate, iodine or tetrabutylammonium fluoride/boron trifluoride complex for example. Other variations of the reaction conditions detailed above for the protection and deprotection steps, as may be readily apparent to the skilled reader, shall be encompassed within the scope of the invention.
In the case of the process for the 1,3-dinitrate, it is hypothesised that the nitration reaction involves addition of a nitronium ion at the epoxide oxygen, followed by an intramolecular rearrangement producing a stable intermediate dioxalenium salt. This is then attacked by the nitrate anion to give (unexpectedly) the 1,3-dinitrato compound.
The invention is now further described with reference to the accompanying examples.
Preparation of Glycerol-l,2-Dinitrate
Example 1 - Preparation of Glycidol t-Butyldimethylsilyl Ether
A three-necked round-bottom flask (100 cm3) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidol (0.74 g, 10 mmol) in dry dichloromethane (DCM)(30 cm3) followed by the addition of t-butyldimethylsilyl chloride (1.65 g, 11 mmol) in dichloromethane (30 cm3) at 0°C via the pressure equalised dropping funnel. The reaction was allowed to stir for 30 minutes before slow addition of triethylamine (1.11 g, 11 mmol in 10 cm3 of DCM). The reaction was then allowed to stir at ambient temperature overnight, after which pentane (30 cm3) was added and the mixture filtered. The filtrate was concentrated and the residue distilled on a kugelrohr to give the product in almost quantitative yield (98%). Example 2 - Nitration of Glycidol t-Butyldimethylsilyl Ether
A three-necked round-bottom flask (100 cm3) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidol t-butyldimethylsilyl ether (0.36 g, 2 mmol) in dry dichloromethane (20 cm3) followed by N2O5 (0.33 g, 3 mmol) in dichloromethane (20 cm3) at 0°C. The reaction was allowed to stir for 2 h at 0°C and then at ambient for a further 1 h. The reaction was quenched with saturated sodium bicarbonate solution (30 cm3) and stirred for a further 15 minutes, separated, dried and the solvent removed to give the glycerol- 1 ,2-dinitrate-3 -t-butyldimethylsilyl ether derivative in 89% yield as a yellow oil.
'H nmr (CDC13): δ 4.83 (IH, dd, 2J = 12.79, 3J = 4.20 Hz, CH2ONO2), 4.64 (IH, dd, 2J = 12.83 and 3J = 6.82 Hz, CH2ONO2), δ 3.89 (IH, dd, 2J = 5.09, 3J = 1.72 Hz, CH2OSi), 3.88 (IH, dd, 2J = 5.09 and 3J = 2.09 Hz, CH2OSi), 3.32 (IH, m, CHONO2), 0.89 (9H, CMe3) and 0.09 (6H, SiMe2). 13C nmr 69.08 (Cl), 78.71 (C2), 59.65 (C3), 25.42 (CMe3) and 17.94 (SiMe2).
Example 3 - Deprotection of Glycerol- l,2-Dinitrate-3-t-Butyldimethylsilyl Ether
A single-neck round-bottom flask (10 cm3) was charged with glycerol- 1,2- dinitrate-3-t-butyldimethylsilyl ether [2 cm3 of IM solution in acetonitrile (0.59 g, 2 mmol)]. 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone, DDQ [2 cm3 of IM solution in acetonitrile: water (9:1), 2 mmol)] was added and the mixture stirred overnight. The mixture was then passed through a silica column (1 g) and the remaining residue washed with fresh ethyl acetate (5 cm3) and also passed through the column. The mixture was concentrated under vacuum to give glycerol- 1,2-dinitrate in 92% yield.
'H nmr (CDC13) δ 4.86 (IH, dd, 2J = 12.0, 3J = 4.30 Hz, CH2ONO2), 4.43 (IH, dd, 2J = 12.0 and 3J = 5.80 Hz, CH2ONO2), δ 3.96, (2H, m, CH2OH), 5.38 (IH, m, CHONO2). 13C nmr 69.12 (Cl), 79.39 (C2), 59.91 (C3). Preparation of Glycerol-l,3-Dinitrate
Example 4 - Preparation of Glycidyl Acetate
A three-necked round-bottom flask (100 cm3) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidol (1.16 g, 10 mmol) in dry dichloromethane (30 cm3) followed by acetyl
chloride (0.86 g, 11 mmol) in dichloromethane (30 cm3) at 0°C via the pressure equalised dropping funnel. The reaction was allowed to stir for 30 minutes before slow addition of triethylamine (1.11 g, 11 mmol in 10 cm3 of DCM). The reaction was then allowed to stir at ambient temperature overnight, after which pentane (30 cm3) was added and the mixture filtered. The filtrate was concentrated and the residue distilled on a kugelrohr to give the product in almost quantitative yield (98%).
Example 5 - Nitration of Glycidyl Acetate
A three-necked round-bottom flask (100 cm3) was equipped with a stirrer bar, alcohol thermometer and a pressure equalised dropping funnel. The flask was charged with glycidyl acetate (0.23 g, 2 mmol) in dry dichloromethane (20 cm3) followed by N2O5 (0.33 g, 3 mmol) in dichloromethane (20 cm3) at 0°C. The reaction was allowed to stir for 2 h at 0°C and then at ambient for a further 1 h.
The reaction was quenched with saturated sodium bicarbonate solution (30 cm3) and stirred for a further 15 minutes, separated, dried and the solvent removed to give the product in almost quantitative yield (95%) as a yellow oil.
Η nmr (CDC13) δ 4.71, (2H, dd 2J = 12.50, 3J = 4.01 Hz, CH2ONO2), 4.59 (2H, dd, 2J = 12.48 and 3J = 5.83 Hz, CH2ONO2), 5.37 (IH, m, CHOCOCH3) and 2.12, (3H, s, OCOCH3). 13C nmr 69.65 (Cl and 3), 66.24 (C2), 20.44 (Me) and 169.81 (CO). Mass spectrum (CI-NH3), 242 (10, M + NH4+), 225 (15, M + H+), 162 (75,H - ONO2), 116 (38, M+ - ONO2- NO2) and 46 (100, NO2 +).
Example 6 - Deprotection of Glycerol-2-Acetoxy-l,3-Dinitrate
A single-necked round-bottom flask (10 cm3) was charged with glycerol-2- acetoxy- 1,3-dinitrate (0.42 g, 2 mmol)] and methanol (10 cm3). Potassium carbonate (0.055 g, 0.4 mmol in 1 cm3 of water was added and the mixture stirred for 4 h. The mixture was then extracted with DCM (2 x 10 cm3), separated and the organic layers combined, dried and the solvent removed in vacuo to give a 93% yield of the glycerol- 1,3-dinitrate.
Η nmr (CDC13) δ 4.62, (2H, dd 2J = 11.70, 3J = 4.26 Hz, CH2ONO2), 4.55 (2H, dd, 2J = 11.70 and 3J = 6.25 Hz, CH2ONO2), 4.41 (IH, m, CHOH) and 3.22, (OH, br). 13C nmr 72.42 (Cl and 3), 65.40 (C2).

Claims

Claims
1. A process for the preparation of glycerol 1 ,2- or glycerol 1 ,3-dinitrate from glycidol which comprises the steps of:
a) preparing either the acetate derivative of glycidol where the desired product is the 1,3-dinitrate or a trialkylsilyl ether derivative (as herein defined) where the desired product is the 1.2-dinitrate;
b) reacting the glycidol derivative from step (a) with dinitrogen pentoxide under anhydrous conditions in order to form the corresponding dinitrato compound; and
c) removing the protective group from the product of step (b) to obtain the glycerol 1,2-dinitrate or glycerol 1,3-dinitrate product as the case may be.
2. A process for the preparation of glycerol 1,3-dinitrate from glycidol which comprises the steps of:
a) preparing the acetate derivative of glycidol;
b) reacting the glycidol acetate from step (a) with dinitrogen pentoxide under anhydrous conditions in order to form the corresponding 1,3-dinitrato compound; and
c) removing the acetate protective group from the product of step (b) to obtain the glycerol 1,3-dinitrate product.
3. A process as claimed in claim 1 or claim 2 wherein the acetate derivative of glycidol is prepared by reacting glycidol with acetyl chloride or acetyl bromide in the presence of triethylamine at about 0°C or by reacting with acetic anhydride in the presence of trimethylsilyl trifluoromethanesulphonate.
4. A process as claimed in any of claims 1 to 3 wherein the acetate protective group is removed by reacting the product of step (b) with potassium carbonate in methanol, iodine in methanol, p-toluenesulphonic acid in methanol or hydrochloric acid in methanol.
5. A process for the preparation of glycerol 1,2-dinitrate from glycidol which comprises the steps of:
a) preparing a trialkylsilyl ether derivative (as herein defined) of glycidol;
b) reacting the trialkylsilyl ether derivative from step (a) with dinitrogen pentoxide under anhydrous conditions in order to form the corresponding dinitrato compound; and
c) removing the trialkylsilyl ether protecting group from the product of step (b) to obtain the glycerol 1 ,2-dinitrate product.
6. A process according to claim 1 or claim 5 wherein the trialkylsilyl ether derivative is prepared by reacting glycidol with the corresponding trialkylsilyl chloride in the presence of triethylamine at a temperature of about 0°C.
7. A process according to claim 1 , 5 or 6 wherein the trialkylsilyl ether protective group is removed by reacting the product of step (b) with 2,3-dichloro-5,6- dicyano-l,4-benzoquinone (DDQ), lithium chloride in dimethylformamide, eerie ammonium nitrate, iodine or tetrabutylammonium fluoride/boron trifluoride complex.
8. A process as claimed in any of claims 1, 5, 6 or 7 wherein the trialkylsilyl in the trialkylsilyl ether derivative is butyldimethylsilyl.
9. A process substantially as described herein and with reference to the examples.
PCT/GB2000/002515 1999-07-03 2000-06-26 Process for the production of glycerol dinitrates WO2001002336A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU55576/00A AU5557600A (en) 1999-07-03 2000-06-26 Process for the production of glycerol dinitrates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9915558.2 1999-07-03
GB9915558A GB2352239A (en) 1999-07-03 1999-07-03 Preparation of Glycerol Dinitrates

Publications (1)

Publication Number Publication Date
WO2001002336A1 true WO2001002336A1 (en) 2001-01-11

Family

ID=10856557

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/002515 WO2001002336A1 (en) 1999-07-03 2000-06-26 Process for the production of glycerol dinitrates

Country Status (3)

Country Link
AU (1) AU5557600A (en)
GB (1) GB2352239A (en)
WO (1) WO2001002336A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101665434B (en) * 2009-09-15 2012-09-05 天津大学 Safe separation and purification method of nitrate ester
WO2014193314A3 (en) * 2013-05-31 2015-01-22 Slovenská Technická Univerzita V Bratislave Additive for cetane number increase of diesel fuels and bio-diesel fuels and its use

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181124A (en) * 1982-07-15 1987-04-15 Secr Defence Process for producing high energy materials
EP0223440A1 (en) * 1985-10-25 1987-05-27 The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and A process for the production of high energy material
GB2317172A (en) * 1996-09-05 1998-03-18 Secr Defence Dinitrate esters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181124A (en) * 1982-07-15 1987-04-15 Secr Defence Process for producing high energy materials
EP0223440A1 (en) * 1985-10-25 1987-05-27 The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and A process for the production of high energy material
GB2317172A (en) * 1996-09-05 1998-03-18 Secr Defence Dinitrate esters

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DAVIES, ALWYN G. ET AL: "An electron spin resonance study of 3- oxypropenoyl radicals derived from glycidols", J. CHEM. SOC., PERKIN TRANS. 2 (1981), (8), 1132-7, XP002152850 *
EREMENKO L T ET AL: "O-nitration of primary and secondary unsaturated and alpha-epoxy alcohols", BULLETIN OF THE ACADEMY OF SCIENCES OF THE USSR. DIVISION OF CHEMICAL SCIENCE., vol. 1, 1967, CONSULTANTS BUREAU. NEW YORK., US, pages 1104 - 1106, XP000964576 *
GUO, JIASHENG ET AL: "Total synthesis of altohyrtin A (Spongistatin 1): part 1", ANGEW. CHEM., INT. ED. (1998), 37(1/2), 187-192, XP002131642 *
PIACENZA, G. ET AL: "Molecular mechanics versus volume additivity methods in prediction of energetic materials density. Comparative analysis, and improvements for solids and liquids", INT. ANNU. CONF. ICT (1997), 28TH(COMBUSTION AND DETONATION), 123.1-123.14, XP000964599 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101665434B (en) * 2009-09-15 2012-09-05 天津大学 Safe separation and purification method of nitrate ester
WO2014193314A3 (en) * 2013-05-31 2015-01-22 Slovenská Technická Univerzita V Bratislave Additive for cetane number increase of diesel fuels and bio-diesel fuels and its use

Also Published As

Publication number Publication date
AU5557600A (en) 2001-01-22
GB2352239A (en) 2001-01-24
GB9915558D0 (en) 1999-09-01

Similar Documents

Publication Publication Date Title
CA2004355A1 (en) Process for intermediate compounds for preparing penems and carbapenems
WO2001002336A1 (en) Process for the production of glycerol dinitrates
JPS5995231A (en) Manufacture of optically active compound
Ishimaru et al. Lewis acid-catalyzed [4+ 2] type cycloadditions of aldimines bearing α-hydrogens with 2-silyloxy-1, 3-butadienes
EP0528209B1 (en) Process for preparing intermediates for vitamin D derivatives and compounds obtained thereby
Utimoto et al. The rate enhancement effect of protodesilylation of arylsilane derivatives
Frankel et al. Synthesis of novel energetic compounds. V. The use of acetyl azide as an" azidation agent"
US5225569A (en) Process for precursors to calcitriol and related compounds
JP4399885B2 (en) Method for producing 4-methyltetrafluorobenzyl alcohol derivative
US4772695A (en) Process for the preparation of vinyl carbamates
JP3773578B2 (en) Taxol synthetic intermediate
JP3055273B2 (en) Method for producing 5-methylene-2-substituted-2-cyclopenten-1-one
EP0238252B1 (en) Preparation of azetidinones and intermediates
EP0514148B1 (en) Manufacture of N-tert-butyldialkylsilylmaleimide
JP3249847B2 (en) Method for producing Z-cyclohexylideneacetic acid derivative
CA1112658A (en) CYCLISATION SUBSTRATES CONVERTIBLE TO 7-.alpha.- SUBSTITUTED 19-NORSTEROID DERIVATIVES
JP3712077B2 (en) Hydroindan-4-ol derivative and method for producing the same
CH655716A5 (en) CHIRAL CYCLOPENTENE DERIVATIVES AND PROCESSES FOR THEIR PREPARATION.
KR100679115B1 (en) Process for preparing 1-alpha-hydroxycholecalciferol derivatives
JP2720176B2 (en) Method for producing panaxacols
JPS6151575B2 (en)
JP2975705B2 (en) Steroid derivatives
JP4158228B2 (en) Process for producing cyclopentenone derivative and cyclopentenone derivative
JPH05186420A (en) Production of 1alpha,25-dihydroxycholecalciferol
JPH0316338B2 (en)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP