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CA2117435A1 - Preparation of 2-amino-6-chloropurine - Google Patents

Preparation of 2-amino-6-chloropurine

Info

Publication number
CA2117435A1
CA2117435A1 CA002117435A CA2117435A CA2117435A1 CA 2117435 A1 CA2117435 A1 CA 2117435A1 CA 002117435 A CA002117435 A CA 002117435A CA 2117435 A CA2117435 A CA 2117435A CA 2117435 A1 CA2117435 A1 CA 2117435A1
Authority
CA
Canada
Prior art keywords
chloropurine
amino
acyl group
guanine
phase transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002117435A
Other languages
French (fr)
Inventor
Christopher R. J. Killen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SmithKline Beecham Ltd
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2117435A1 publication Critical patent/CA2117435A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D473/00Heterocyclic compounds containing purine ring systems
    • C07D473/40Heterocyclic compounds containing purine ring systems with halogen atoms or perhalogeno-alkyl radicals directly attached in position 2 or 6

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for preparing 2-amino-6-chloropurine comprises reacting a 2,9-diacylated derivative of guanine with a chlorinating agent in the presence of a phase transfer catalyst containing chloride ions, and thereafter removing the 9-acyl group and the 2-acyl group by hydrolysis.

Description

CA21 i 7435 W O 93/15075 Pc~r/GB93/00185 Preparatton of 2-am~no-6-chloropurtne This invention relates to a process for the pr~pardl;on of a compound usetul 5 as an i" -", in the pr~:pd, n of phd""aceutical compounds.

The compound 2-amino-6-chloropurine of formula (I):
a <NX~ N

H N NHz 1 0 (1) is a useful i" ". in the pr.ra. ) of nucleoside analogue antiviral agents such as penciclu~i. and fdlllci(.luJi. described in EP-A-141927 (Example 1) and EP-A-182024 (Example 2). The illl~:r",e.lidlt~ is 15 9-s~ with an d~plupridle side chain precursor followed by conversion of the 6-chloro moiety to a hydroxy (a guanine) or hydrogen (a 2-aminopurine).

EP-A-203685 (Beecham Group p.l.c.) describes a process for preparing a 20 compound of fommula (I) as he,_;.,L.~ful~ defined which process cu",plises reacting guanine with a cl,lu,i,,dling agent in the presence of a phase transfer catalyst containing chloride ions. EP-A-433846 (Hoechst A~iengesel sul,dfl) describes a .;ur,~,:,uoncling process for preparing the 2-acylated derivative involving cl,lor", .~ of 2 9-diacylguanine and subsequent removal of the 9-25 acyl group by hydrolysis.

The reaction is preferably carried out in a polar inert organic solvent such asace~u,,it,ild tetrahydrofuran dioxan nil~u,,,~ll,ane diglyme dimethoxyethane ordicl,lo,u,,,~ll,ane. Acetonitrile is highly preferred.

CA 2 ~ 17~35 W O 93/15075 P(~r/G B93/00185 Suitable phase transfer catalysts include tetr~c~ Ihs~it~ d ammonium chlorides. Examples of ammonium substituents include C2-1 2 alkyl, usually C2 4 alkyl, or phenyl or benzyl. Other possible phase transfer catalysts include tetra-sl l~ - I ' pho:,,uhonium chlorides wherein examples of the 5 sl l~ l Itb are as defined above for ammonium chlorides. Fl ~ferdu' y the phase transfer catalyst is tetraethylammonium chloride.

The phase-transfer catalyst is preferably present in an amount of from 1 to 3 equivalents of the compound of formula (Il) and preferably from 1 to 2 1 0 equivalents.

A preferred chlu,i,ldtil,9 agent is phosphonus oxychloride.

Preferably the ~;hlo,i,l ,9 agent is present in an amount of from 2-10 15 preferably from 3-6 molar equivalents of the guanine derivative.

The reaction may be effected in the presence of a weak base, such as a tertiary amine, for example N,N-dimethylaniline or diethylaniline or triethylamine. The base is usually present in an d~,uru,~i".~2~1y molar 20 equivalent amount with respect to the guanine derivative. A!:_r" ' ~/~,ly, a catalytic amount of water may be added to the reaction mixture. When ac.i~u,,il,ile is the solvent, added base may not be necessary, but is preferred.

25 The reaction is preferably carried out at an elevated temperature of from 30-1 00~C, most preferably under reflux and/or with u lt d~onicdtion at 50-70~C.

Preferably the reaction is allowed to proceed for a period of greater than half 30 an hour, usually less than 30 hours.

We have now discovered that the compound of formula (I) may be prepared from 2,9-diacylguanine.

W O 93/15075 PC~r/G B93/0018S
Accordingly, the present invention provides a process for preparing 2-amino-6-chloropurine, which process comprises reacting a 2,9-diacylated derivative of guanine with a cl,loli"dli,)g agent in the presence of a phase transfer catalyst co"' , ,9 chloride ions, and thereafter removing the 9-acyl group 5 and the 2-acyl group by hydrolysis.

The reaction is described in EP-A-203685 and EP-A-433846, which are illcor~ordtdd herein by reference, except that methyltriethylammonium chloride is a preferred phase transfer catalyst; the amount of phosphorus 10 oAychlorida may be reduced to 2-4 equivalents, and the reaction time can be reduced.

If the removal of the 9-acyl group generally occurs at ambient temperature (below 30~C), but higher temperatures and reaction times (80-100~C, 1 -2 15 hours) are needed for removal of the 2-acyl group. Aqueous sodium hydroxide is a suitable basic medium for the hydrolysis.

The following example illustrates the invention.

Example Diacetyl guanine (8.09, 0.034 moles), triethylmethylammonium chloride (15.459, 0.102 moles), and llit:lllyldlll;ne (4.74 mls, 0.034 moles) were 25 heated together with stirring in ac~lu,,il~ild (70mls) to 50~C. Phosphorus o,~y~ loride (6.34 mls, 0.068 moles) was then added and stirring continued for 4 hours. The reaction mixture was cooled and then added to aqueous sodium hydroxide solution (209 in 300mls water). The reaction mixture was heated to 80~C for 2 hours and then the volume made up to 300 mls with 30 water. The mixture was cooled to 25~C and the pH adjuster to 7 using 10~/O
hJd~ hloiic acid. The resulting slurry was stirred for fifteen minutes and the product filtered off and washed with water 30 mls and then dried at 80~C
under vacuum to give a cream/off white coloured product.

35 Weight 2-amino-6-chloropurine 4.69 9 (74.6% yield).

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing 2-amino-6-chloropurine, which process comprises reacting a 2,9-diacylated derivative of guanine with a chlorinating agent in the presence of a phase transfer catalyst containing chloride ions, and thereafter removing the 9-acyl group and the 2-acyl group by hydrolysis.
2. A process according to claim 1, wherein the chlorinating agent is phosphorus oxychloride and the phase transfer catalyst is methyltriethylammonium chloride.
3. A process according to in claim 2, wherein the amount of phosphorus oxychloride is 2-4 equivalents with respect to the 2,9-acylated guanine.
4. A process according to claim 1, wherein aqueous sodium hydroxide is used as the basic medium for the hydrolysis.
5. Famciclovir or penciclovir whenever prepared from 2-amino-6-chloropurine prepared according to the process of claim 1.
CA002117435A 1992-01-30 1993-01-28 Preparation of 2-amino-6-chloropurine Abandoned CA2117435A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9201961.1 1992-01-30
GB929201961A GB9201961D0 (en) 1992-01-30 1992-01-30 Pharmaceuticals

Publications (1)

Publication Number Publication Date
CA2117435A1 true CA2117435A1 (en) 1993-08-05

Family

ID=10709516

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002117435A Abandoned CA2117435A1 (en) 1992-01-30 1993-01-28 Preparation of 2-amino-6-chloropurine

Country Status (10)

Country Link
EP (1) EP0625154A1 (en)
JP (1) JPH07503246A (en)
KR (1) KR950700299A (en)
AU (1) AU669874B2 (en)
CA (1) CA2117435A1 (en)
GB (1) GB9201961D0 (en)
MX (1) MX9300482A (en)
NZ (1) NZ246677A (en)
WO (1) WO1993015075A1 (en)
ZA (1) ZA93615B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4231036A1 (en) * 1992-09-17 1994-03-24 Basf Ag Process for the preparation of 2-amino-6-halopurines
JPH07133276A (en) * 1993-09-17 1995-05-23 Jiyuuzen Kagaku Kk Production of 2-acetylamono-6-chloropurine
DE4415196C1 (en) * 1994-04-30 1995-04-27 Boehringer Ingelheim Kg Improved process for the preparation of 2-amino-6-chloropurine and 2-acylamino-6-chloropurines
CA2189088C (en) * 1995-11-09 2005-09-20 Masatoshi Sakai 2-amino-6-chloropurine and method for preparing the same
EP1490369B1 (en) * 2002-04-04 2007-11-14 Sumitomo Chemical Company, Limited Production method of 2,6-dihalopurine
CN102336755B (en) * 2011-09-30 2013-03-27 浙江工业大学 Chemical synthesis method of 6-chloropurine
CN113214260B (en) * 2021-05-10 2022-04-01 上海凌凯医药科技有限公司 Synthesis method of 2-acetamido-9-acetyl purine

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3485225D1 (en) 1983-08-18 1991-12-05 Beecham Group Plc ANTIVIRAL GUANINE DERIVATIVES.
EP0182024B1 (en) 1984-09-20 1991-04-03 Beecham Group Plc Purine derivatives and their pharmaceutical use
GB8507606D0 (en) * 1985-03-23 1985-05-01 Beecham Group Plc Process
DE3941658A1 (en) * 1989-12-16 1991-06-20 Hoechst Ag METHOD FOR PRODUCING 2-ACYLAMINO-9-ACYL-6-HALOGEN PURIN
DE3941657A1 (en) 1989-12-16 1991-06-20 Hoechst Ag METHOD FOR PRODUCING 2-ACYLAMINO-6-HALOGEN PURINE FROM 2,9-DIACYLGUANINE
GB9102127D0 (en) * 1991-01-31 1991-03-13 Smithkline Beecham Plc Pharmaceuticals

Also Published As

Publication number Publication date
EP0625154A1 (en) 1994-11-23
NZ246677A (en) 1996-02-27
KR950700299A (en) 1995-01-16
MX9300482A (en) 1994-07-29
GB9201961D0 (en) 1992-03-18
ZA93615B (en) 1993-11-26
JPH07503246A (en) 1995-04-06
AU669874B2 (en) 1996-06-27
AU3365493A (en) 1993-09-01
WO1993015075A1 (en) 1993-08-05

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