Organic Syntheses / Process Chemistries

1. LINAS R. STASAITIS
190 Stephens Lane
Fairfield, CT 06824-5445
Phone: (203) 332-1930 Lstasaitis@prodigy.net
Organic Synthesis Research Summaries
US Patent 5,420,362: Synthesis of 2-Methyl-1-naphthol
OH OH N OH
HCHO H2
Me2NH Pd/C
Cl Cl
99.5% yield 95% yield
US Patent 5,486,619: Method of Producing DAI from DOPA, Using One Reaction Vessel
HO CO2H O CO2H HO
NaHCO3
NH2 NH2
HO K3Fe(CN)6 O HO N CO2H
H
O HO AcO
Ac2O
+
HO N CO2H HO N triethanolamine AcO N
H H
51 % yield
US Patents 5,520,707: Methods for Dyeing Hair with Anthraquinones having a Quarternary
5,891,200 Ammonium Side Chain
O HN O HN O HN O HN
NBS Cu iodoalkane
Amine
O O Br O HN O HN
I
NR1R2 NR1R2R3
+

2. LINAS R. STASAITIS Page Two
US Patents 5,529,583: Storage Stable 2-Methyl-1-Naphthol Couplers
5,672,180
6,045,590
OH OR1 O OH
TEA Zn
acetylating H2SO4
agent HOR2
O OR2
US Patent 5,670,698: Synthesis of 1-Acetoxy-2-Methylnaphthalene
OH OH N OAc OAc OAc
formaldehyde Ac2O H2
piperidine Pd/C
99.4% yield 86% yield
US Patent 5,865,954: Bis-(2-4-Diaminophenoxy)Benzenes and their use as Coupling Components in Oxidative Hair
Coloring Compositions and Methods
F
HO OH NO2 O O H2 O O
K2CO3
+ Pd/C
O 2N NO2 O2N NO2 H2N NH2 H2N NH2
NO2
US Patent 5,980,584: Substituted p-Aminophenol, Process of Preparation and Use in Dyeing Hair
O O OH O OH OH OH OH
O 2N OH OH OH
HNO3 NaOH H2
O O
N O BH3:THF
N H2SO4 Pd/C
H H
NO2 NO2 NH2
100% yield 94.4% yield 100% yield

3. LINAS R. STASAITIS Page Three
US Patent 6,200,353: Coupler for Use in Oxidative Hair Dyeing
R1
O
R R
OH X OH
H
NaBH4 R1
NH2 HN
X
US Patent 6,228,130: Primary Intermediate in Oxidative Hair Dyeing
O NH2 O NH2 OH NH2 OH
O 2N ONa OH OH
NaOH H2
O
N O BH3:THF Pd/C
H
NO2 NO2 NH2
100% yield 98.6% yield 81.8% yield
US Patent 6,342,079: Primary Intermediate in for use in Oxidative Hair Dyeing
O O
NH2 O NH O NH O
HNO3
6 N HCl
Acetic Anhydride H2SO4
NO2
88% yield 65% yield
NH2 O NH2 OH NH2 OH
6 N HCl NaBH4 H2
Pd/C
NO2 NO2 NH2
79% yield 99% yield 100% yield
US Patent 6,540,793: Coupler for Use in Oxidative Hair Dyeing
R H R
OH (R1)y Ar C O OH
NaB(OAc)3 or NaBH4
NH2 NH
Ar (R1)y

4. LINAS R. STASAITIS Page Four
US Patents 2004/016859 & WO 04111011A2: Synthesis of 2-Aryl Pyrimidine 4-Carboxylic Acid Amides
NH
Cl
NH2
+
O
F
O Amidine O O
O O
O O O
O N N
O
oxobutyraldehyde dimethylacetal O O NH2
enol ether enamide
enamine
NaOMe, MeOH
N
Cl
N
O 1, 4 dioxane EtOH, NaOEt
F
(70 %)
SeO2 / Pyridine EtOH, NaOEt
N N
Cl Cl O
N CO2H N
O
O O
H2SO4 / EtOH
F F
(92 %) NH3 / EtOH
N
Cl NH2
N
O
O
F